CN103112991A - Coking wastewater treatment system and coking wastewater treatment method - Google Patents

Coking wastewater treatment system and coking wastewater treatment method Download PDF

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CN103112991A
CN103112991A CN2013100301305A CN201310030130A CN103112991A CN 103112991 A CN103112991 A CN 103112991A CN 2013100301305 A CN2013100301305 A CN 2013100301305A CN 201310030130 A CN201310030130 A CN 201310030130A CN 103112991 A CN103112991 A CN 103112991A
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waste water
chemical waste
coking chemical
coking
level
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CN103112991B (en
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周泽宇
吕小鸿
周湧
周巍
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SHENZHEN LEAGUER ENVIRONMENTAL TECHNOLOGY Co Ltd
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SHENZHEN LEAGUER ENVIRONMENTAL TECHNOLOGY Co Ltd
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Abstract

The invention discloses a coking wastewater treatment system. The system comprises coking wastewater coal car treatment equipment, coking wastewater oxidization and biochemical treatment equipment, and coking wastewater deep treatment equipment, wherein the coking wastewater coal car treatment equipment is used for removing coal tar from the coking wastewater; and the coking wastewater deep treatment equipment is used for deeply treating the coking wastewater. The coking wastewater treatment system has good treatment effect. The invention further provides a coking wastewater treatment method.

Description

Coking wastewater processing system and coking waste water treatment method
Technical field
The present invention relates to a kind of coking wastewater processing system and coking waste water treatment method.
Background technology
Coking chemical waste water has comprised the waste water that produces in gas production, coking, metallurgy and ceramic kiln burning production process, has had high organism, high phenol, high ammonia nitrogen characteristics, what even have also contains cyanogen, suspended substance and colourity are also very high, belong to the organic waste water of high density bio-refractory.The treatment effect of existing coking wastewater processing system is relatively poor.
Summary of the invention
Based on this, be necessary to provide a kind for the treatment of effect coking wastewater processing system and coking waste water treatment method preferably.
A kind of coking wastewater processing system comprises:
Coking chemical waste water coal tar treatment facility, the coal tar for removing coking chemical waste water comprises:
Oil-isolating device is used for removing the larger suspension oil of coking chemical waste water particle;
Air-floating apparatus is communicated with described oil-isolating device, and described air-floating apparatus is used for removing the larger suspended substance of coking chemical waste water; And
The acid out device is communicated with described air-floating apparatus, and described acid out device is used for further removing the coal tar of coking chemical waste water;
Coking chemical waste water oxidation and biochemical processing device comprise:
The one-level electrocatalysis oxidation apparatus is communicated with described acid out device, and described one-level electrocatalysis oxidation apparatus is used for coking chemical waste water is carried out catalytic oxidation;
The one-level settler is communicated with described one-level electrocatalysis oxidation apparatus, and described one-level settler is for the precipitation of removing coking chemical waste water;
Transition apparatus is communicated with described one-level settler, and described transition apparatus is used for accommodating the coking chemical waste water of processing through described one-level settler;
Anaerobic device is communicated with described transition apparatus, and described anaerobic device is used for coking chemical waste water is carried out anaerobic biological treatment;
Hypoxia device is communicated with described anaerobic device, and described hypoxia device is used for that described coking chemical waste water is carried out biological denitrification to be processed;
Aerobic device is communicated with described hypoxia device, and described aerobic device is used for described coking chemical waste water is carried out aerobic treatment;
The secondary electrocatalysis oxidation apparatus is communicated with described aerobic device, and described secondary electrocatalysis oxidation apparatus is used for that coking chemical waste water is carried out degree of depth catalytic oxidation to be processed;
The two-stage precipitation device is communicated with described secondary electrocatalysis oxidation apparatus, and described two-stage precipitation device is for the precipitation of removing coking chemical waste water;
BAF is communicated with described two-stage precipitation device; And
Membrane bioreactor is communicated with described BAF;
Coking wastewater deep treatment equipment is used for coking chemical waste water is carried out advanced treatment, comprising:
The one-level rough filtering device is communicated with described membrane bioreactor, and described one-level rough filtering device is used for described coking chemical waste water is carried out the one-level coarse filtration;
The secondary rough filtering device is communicated with described one-level rough filtering device, and described secondary rough filtering device is used for described coking chemical waste water is carried out the secondary coarse filtration;
One-level security personnel filtration unit is communicated with described secondary rough filtering device, and described one-level security personnel filtration unit is used for that coking chemical waste water is carried out the one-level security personnel and filters;
Nanofiltration device is communicated with described one-level security personnel filtration unit, and described nanofiltration device is used for that coking chemical waste water is carried out nanofiltration and processes;
Secondary security personnel filtration unit is communicated with described nanofiltration device, and described secondary security personnel filtration unit is used for that coking chemical waste water is carried out the secondary security personnel and filters; And
Reverse-osmosis filtering device is communicated with described secondary security personnel filtration unit, and described reverse-osmosis filtering device is used for coking chemical waste water is carried out osmosis filtration.
In embodiment, described coking wastewater processing system also comprises the stripping tower that is communicated with the setting device of coking chemical waste water coal tar treatment facility therein, and described stripping tower is used for removing the nitrogen that coking chemical waste water exists with ammonium ion and free ammonia state.
Therein in embodiment, described coking wastewater processing system also comprises sludge treatment device, described sludge treatment device comprises sludge sump and pressure filter, described sludge sump is used for accommodating the precipitation that described air-floating apparatus, described one-level settler, described hypoxia device, described aerobic device, described two-stage precipitation device, described BAF and described membrane bioreactor produce, and the mud that described pressure filter is used for described sludge sump is accommodated carries out press filtration.
A kind of coking waste water treatment method that uses above-mentioned coking wastewater processing system comprises the following steps:
Use the larger suspension oil of particle in oil-isolating device removal coking chemical waste water;
Use air-floating apparatus to remove suspended substance larger in coking chemical waste water;
Use acid out device is further removed the emulsification shape coal tar in coking chemical waste water;
Use the one-level electrocatalysis oxidation apparatus to carry out catalytic oxidation to coking chemical waste water;
Use one-level settler is removed the precipitation in coking chemical waste water;
Use transition apparatus to regulate the pH value of coking chemical waste water;
Use anaerobic device to carry out anaerobic biological treatment to coking chemical waste water;
Using hypoxia device to carry out biological denitrification to coking chemical waste water processes;
Use aerobic device to carry out aerobic treatment to coking chemical waste water;
Using the secondary electrocatalysis oxidation apparatus to carry out degree of depth catalytic oxidation to coking chemical waste water processes;
Use two-stage precipitation device is removed the precipitation in coking chemical waste water;
Use BAF that coking chemical waste water is processed;
Use membrane bioreactor that coking chemical waste water is processed;
Use the one-level rough filtering device to carry out the one-level coarse filtration to coking chemical waste water;
Use the secondary rough filtering device to carry out the secondary coarse filtration to coking chemical waste water;
Using one-level security personnel filtration unit to carry out the one-level security personnel to coking chemical waste water filters;
Use nanofiltration device to carry out nanofiltration to coking chemical waste water;
Using the secondary protective device to carry out the secondary security personnel to coking chemical waste water filters; And
Using reverse-osmosis filtering device to carry out osmosis filtration to coking chemical waste water processes.
Therein in embodiment, also comprise step after the step of the suspension oil that the particle in described use oil-isolating device removal coking chemical waste water is larger: use setting device to process the coking chemical waste water of process oil-isolating device processing, the coking chemical waste water that enters described air-floating apparatus is homogenized.
Therein in embodiment, also comprise step in described use air-floating apparatus is removed coking chemical waste water before the step of larger suspended substance: the nitrogen that will use through the coking chemical waste water that homogenizes that setting device is processed stripping tower to exist with the form of ammonium ion and free ammonia in removing coking chemical waste water enters described air-floating apparatus after the coking chemical waste water of processing through stripping tower is processed through setting device again.
Therein in embodiment, also comprise step described use secondary rough filtering device carries out the step of secondary coarse filtration to coking chemical waste water after: the coking chemical waste water that will advance the secondary coarse filtration injects the First Transition device, and the coking chemical waste water of processing through the First Transition device re-uses described one-level security personnel filtration unit to carry out the one-level security personnel and filter.
Therein in embodiment, carrying out the step of nanofiltration to coking chemical waste water after, described use nanofiltration device also comprises step, to inject the second transition apparatus through the coking chemical waste water of nanofiltration, the coking chemical waste water of processing through the second transition apparatus re-uses described secondary security personnel filtration unit to carry out the secondary security personnel and filters.
In embodiment, use described one-level electrocatalysis oxidation apparatus that coking chemical waste water is carried out adding FeSO when catalytic oxidation is processed under acidic conditions therein 4And H 2O 2Carry out catalytic oxidation.
In embodiment, use described secondary electrocatalysis oxidation apparatus to be H to the oxygenant that coking chemical waste water carries out using when degree of depth catalytic oxidation is processed therein 2SO 4And H 2O 2
Above-mentioned coking wastewater processing system and coking waste water treatment method can effectively be removed suspended substance, organism and ammonia nitrogen in coking chemical waste water, and the coking chemical waste water of the processing of final output can reach emission standard, and treatment effect is better; After processing through coking chemical waste water coal tar treatment facility, the content of coal tar is lower, can avoid excessive coal tar that follow-up treatment facility is produced and destroy; Coking chemical waste water oxidation and biochemical processing device comprehensive utilization catalytic oxidation and bio-oxidation technology, the effectively organism in treatment of Coking Wastewater; The COD value of the coking chemical waste water of coking wastewater deep treatment device processes is lower, can remove simultaneously the impurity in coking chemical waste water, makes the coking chemical waste water can qualified discharge.
Description of drawings
Fig. 1 is the structural representation of the coking wastewater processing system of an embodiment;
Fig. 2 is the schematic diagram of osmosis filtration treatment process.
Embodiment
For the ease of understanding the present invention, the below is described more fully the present invention with reference to relevant drawings.Provided first-selected embodiment of the present invention in accompanying drawing.But the present invention can realize in many different forms, is not limited to embodiment described herein.On the contrary, providing the purpose of these embodiment is to make to disclosure of the present invention more thoroughly comprehensively.
Need to prove, when element is called as " being fixedly arranged on " another element, can directly can there be element placed in the middle in it on another element or also.When an element is considered to " connection " another element, it can be directly connected to another element or may have simultaneously centering elements.Term as used herein " vertical ", " level ", " left side ", " right side " and similar statement are just for illustrative purposes.
Unless otherwise defined, all technology of using of this paper and scientific terminology are with to belong to the implication that those skilled in the art of the present invention understand usually identical.The term that uses in specification sheets of the present invention herein is not intended to be restriction the present invention just in order to describe the purpose of specific embodiment.Term as used herein " and/or " comprise one or more relevant Listed Items arbitrarily with all combinations.
See also Fig. 1, the coking wastewater processing system 10 of an embodiment comprises coking chemical waste water coal tar treatment facility 100, stripping tower 300, coking chemical waste water oxidation and biochemical processing device 500 and coking wastewater deep treatment equipment 700.
See also Fig. 2, coking chemical waste water coal tar treatment facility 100 is used for removing the coal tar of coking chemical waste water.Coking chemical waste water coal tar treatment facility 100 comprises oil-isolating device 110, setting device 120, air-floating apparatus 130 and acid out device 140.
Oil-isolating device 110 is used for removing the larger suspension oil of coking chemical waste water particle.Contain a large amount of tar in coking chemical waste water, have a strong impact on (after especially oil enters biochemical system, meeting is to greatly reducing the activity of biochemical bacteria) as not removing follow-up materialization is processed to produce.Oil-isolating device 110 is difference of specific gravity of utilizing oil and water, separates a kind of processing structures of removing the suspension oil that in coking chemical waste water, particle is larger.Concrete, oil-isolating device 110 can be for forms such as oil removal case, oil trap or oil separation tanks, as long as can reach the effect of removing the suspension oil that in coking chemical waste water, particle is larger.
The structure of oil-isolating device 110 adopts flat flow more, the coking chemical waste water of oil-containing enters in the pond that the plane is rectangle by distributing trough, the along continuous straight runs sluggish flow, oils floats up to the water surface in flowing, and is pushed to by oil header or the Oil scraper that is arranged on the pond face and then flows into water knockout in oil header.The heavy oil that precipitates in the pond and other impurity accumulate in the pool bottom sludge bucket, enter in sludge tank by shore pipe, and the waste water of processing through oil removal overflow enters discharge channel and discharges outside the pond, carries out subsequent disposal, to remove oil in water emulsion and other pollutents.
Need to prove, coking chemical waste water can use equalizing tank or surge tank (not shown) to process before entering oil-isolating device 110 processing, the waste water that enters oil-isolating device 110 is homogenized, it is stable that thereby assurance enters the water quality of the coking chemical waste water of oil-isolating device 110, therefore, equalizing tank or surge tank can be set before oil-isolating device 110.In present embodiment, the volume ratio of equalizing tank or surge tank and oil-isolating device 110 is 1:5 ~ 1:3.
Setting device 120 is connected with oil-isolating device 110.Setting device 120 is used for accommodating the coking chemical waste water of processing through oil-isolating device 110, the coking chemical waste water that is housed in setting device 120 is homogenized, thereby the water quality that guarantees to enter the coking chemical waste water of air-floating apparatus 130 is stable, thereby can be according to the correlation parameter of the relative parameters setting air-floating apparatus 130 of setting device 120 interior coking chemical waste waters.Setting device 120 can be equalizing tank or surge tank.
Air-floating apparatus 130 is connected with setting device 120.Air-floating apparatus 130 is used for removing the larger suspended substance of coking chemical waste water.Air supporting is to utilize the micro-bubble of high dispersing to remove to adhere to the object of hydrophobic group in waste water for carrier, its small bubbles and object is looked as a whole, and its global density floats to the water surface on less than water, thereby realizes the process that solid-liquid or liquid liquid separate.Air-floating apparatus 130 can for horizontal flow air flotation device or flow lifting type air-floating apparatus, be preferably horizontal flow air flotation device.
The principle that produces according to microbubble is different, air-floating apparatus 130 can be aeration air-floating apparatus, dissolved air flotation device and electrofloatation device, as long as can remove the larger suspended substance in coking chemical waste water, also at least two in aeration air-floating apparatus, dissolved air flotation device and electrofloatation device series connection can be used as required.
Air-dissolving air-float refers to that air pressurized is dissolved in water and reaches capacity, and the decompression of dissolved air water stream disengages microbubble when entering air flotation pool.Pressure air-dissolving water can be all or part of of the water of processing, can be also the recirculation water of air flotation pool water outlet, and the per-cent that the backflow water yield accounts for the water yield of processing claims reflux ratio, is the important factor that affects daf efficiency, must be determined by test.The equipment of pressure air-dissolving method has force (forcing) pump, dissolving and air compressor etc.Dissolving is the pressure-bearing steel cylinder, inner standing flow deflector or the placement filler put.The dissolving water outlet enters air flotation pool by reducing valve or reliever.
Acid out device 140 is communicated with air-floating apparatus 130.Acid out device 140 is used for further removing the emulsification shape coal tar of coking chemical waste water.Acid out is under acidic conditions, and the part material is become suspended state from dissolved state or colloidal state, then separates (using precipitation or air supporting).In present embodiment, acid out is with acid (hydrochloric acid or sulfuric acid), the oil in water emulsion in water to be become suspended matter.Need to prove, acid out can be acid out device independently, also can add the acid out function on the equipment such as settling tower, air supporting, and the chemicals dosing plant that is exactly in fact an acid adding agent adds stirrer.
After coking chemical waste water is processed through coking chemical waste water coal tar treatment facility 100, the content of coal tar in 20mg/L, can be avoided excessive coal tar that follow-up treatment facility is produced and destroy.
Stripping tower 300 is communicated with setting device 130.Stripping tower 300 is used for removing coking chemical waste water with ammonium ion (NH 4+) and free ammonia (NH 3) nitrogen that exists of state.
NH 4+And NH 3Equilibrium relationship as follows:
NH 3+H 2O→NH 4++OH -
This equilibrium relationship is subjected to the impact of pH value, and when the pH value was high, balance was moved to the left, and the ratio of free ammonia increases.During normal temperature, the ammonia nitrogen great majority exist with the ammonium ion state when the pH value is 7 left and right, and pH is when being 11 left and right, and free ammonia roughly accounts for 98%, and free ammonia is easy to overflow from water, as aeration in addition, can impel ammonia to overflow from water, and wherein, pH is that effect is crucial.
At different pH, temperature, the rate of dissociation (%, the i.e. separation rate of free ammonia and water) of ammonia nitrogen is as shown in the table
pH 20℃ 30℃ 35℃
9.0 25 50 58
9.5 60 80 83
10.0 80 90 93
11.0 98 98 98
Generally, the structure of stripping tower 300 adopts gas-liquid contact apparatus, fills filler in the inside of tower, in order to improve contact area.Regulate that water after pH value is showered into from the top of tower on filler and the formation water droplet, gap along filler falls one after another, contact with the air inversion that is upwards blowed at the bottom of the tower by blower fan, complete mass transfer process, make ammonia transfer gas phase to by liquid phase, with air venting, complete the stripping process, decreasing ratio reaches more than 75%.Low concentration wastewater is used air stripping usually at normal temperatures, and high-concentration waste water is everlasting and is carried out stripping under warm-up mode.
Ammonia gas subsequent after stripping enters the ammonia type absorption purification tower, makes ammonia and absorption liquid produce chemical reaction in tower, can make gas qualified discharge, pollution-free.
Need to prove, setting device 120 can be omitted, and this moment, oil-isolating device 110 directly was communicated with air-floating apparatus 130, and the coking chemical waste water of processing by oil-isolating device 110 this moment directly enters in air-floating apparatus 130 to be processed; Or oil-isolating device 110 is communicated with stripping tower 300, stripping tower 300 is communicated with air-floating apparatus 130, the coking chemical waste water of processing by oil-isolating device 110 this moment enters in stripping tower 300 to be processed, and the coking chemical waste water that process stripping tower 300 is processed enters air-floating apparatus 130 and processes.
Coking chemical waste water oxidation and biochemical processing device 500 comprise one-level electrocatalysis oxidation apparatus 510, settler 520, transition apparatus 530, anaerobic device 540, hypoxia device 550, aerobic device 560, secondary electrocatalysis oxidation apparatus 570, settling tank 580, BAF 610 and membrane bioreactor 620.
One-level electrocatalysis oxidation apparatus 510 is communicated with acid out device 140.One-level electrocatalysis oxidation apparatus 510 is used for coking chemical waste water is carried out catalytic oxidation, with improve in coking chemical waste water 5 days biochemical oxygen demand (BOD) (BOD5) with the ratio of chemical oxygen demand (COD) (COD), thereby improve the biodegradability of coking chemical waste water.Specifically in the present embodiment, one-level electrocatalysis oxidation apparatus 510 is the catalytic oxidation tower.
The working mechanism of one-level electrocatalysis oxidation apparatus 510 is as follows:
Under acidic conditions, in 6~24V of catalytic oxidation low dc voltage electrostatic field, under the condition that has the catalyzer existence that can efficiently excite the hydroxyl radical free radical ion, after regulating pH≤4, add appropriate FeSO 4And H 2O 2, generate simultaneously the sub-OH of hydroxyl radical free radical, because OH has extremely strong oxidisability, make partial organic substances become CO 2And H 2O, remaining organism is hydrolyzed-acidifying, and the sub-chain rupture of macromole becomes small molecules, further makes small organic molecule be oxidized to organic acid, thereby promotes BOD5/COD ratio, has established the basis of follow-up biochemical treatment.
Catalytic oxidation mechanism:
1. the generation of hydroxyl radical free radical
Fe 2++H 2O 2→Fe 3++·OH+OH
Fe 2++·OH→Fe 3++OHFe 3++H 2O 2→Fe 2++HO 2·+H +
HO 2·+H 2O 2→O 2↑+H 2O+·OH
2. mineralization of organic material
RH+·OH→R·+H 2O
R·+Fe 3+→R ++Fe 2+
R+O 2→ROO+→………→CO 2↑+H 2O
Annotate: R is organic molecule.
Subsequent treatment process " hydrolysis " and " acidifying " effect by anerobe, and follow-up aerobic bacteria digests, the organism after the anaerobism are resolved into CO by the aerobic bacteria absorption as nutriment 2And H 2O。
One-level settler 520 is communicated with one-level electrocatalysis oxidation apparatus 510.One-level settler 520 is for the precipitation of removing coking chemical waste water.Add caustic soda in one-level settler 520, caustic soda can be regulated the pH value of coking chemical waste water, enter the coking chemical waste water pH value of one-level electrocatalysis oxidation apparatus 510 generally 3.5 ~ 4, coking chemical waste water pH value after one-level electrocatalysis oxidation apparatus 510 catalytic oxidations are processed rises to 4.5 left and right, therefore can regulate according to the needs of subsequent processing steps the pH value of coking chemical waste water.Different according to demand, one-level settler 520 can be the various ways such as settling tower, settling tank, settler.
Transition apparatus 530 is communicated with settler 520.Transition apparatus 530 is used for accommodating the coking chemical waste water of processing through one-level settler 520, and regulates the pH value of the coking chemical waste water that is housed in transition apparatus 530.In present embodiment, the pH value that is housed in the coking chemical waste water of transition apparatus 530 is adjusted to 6.5 ~ 7.5.Need to prove, transition apparatus 530 can be transition pond or transition case, and the pH value that is housed in transition apparatus 530 is not limited to be adjusted to 6.5 ~ 7.5, regulates according to the requirement of subsequent disposal the pH value that is housed in the coking chemical waste water in transition apparatus 530.Need to prove, also can be chosen in a pH value of regulating coking chemical waste water in one-level settler 520 and transition apparatus 530.
Anaerobic device 540 is communicated with transition apparatus 530.Anaerobic device 540 is used for coking chemical waste water is carried out anaerobic biological treatment.Coking chemical waste water is carried out anaerobic biological treatment, thereby the organic substance decomposing in coking chemical waste water is converted into inorganics.Anaerobic device 540 is anaerobic pond or anaerobic box.
Anaerobic waste water biological treatment refers under condition of free-dioxygen the various complicated organic substance decomposing in waste water to be changed into the process of the materials such as methane and carbon dioxide by the anaerobion effect of (comprising facultative microbe), also claims anaerobic digestion.The fundamental difference of anaerobic waste water biological treatment and aerobic processes is not with molecular oxygen as hydrogen acceptor, and take combined oxygen, carbon, sulphur, nitrogen etc. as hydrogen acceptor.
Anaerobic biological treatment is the chemistry of micro-organisms process of a complexity, relies on the bacterium of three large main monoids, and the combined action that namely is hydrolyzed acid formers, hydrogen-producing acetogenic bacteria and methane-producing bacteria is completed.Thereby roughly anaerobic digestion process is divided into three continuous stages, namely acidication stage, product hydrogen produce the acetic acid stage and produce methane phase.
Fs is the acidication stage.Complicated macromole, insoluble organism first are hydrolyzed to small molecules, dissolved organic matter under the effect of perienzyme, then infiltrate in cell paste, be decomposed into small molecules, dissolved organic matter, then infiltrate in cell paste, decompose generation VFA, alcohols, aldehydes etc.This stage mainly produces than higher fatty acid.
Subordinate phase is produced the acetic acid stage for producing hydrogen.Under the effect of hydrogen-producing acetogenic bacteria, the various organic acids that the fs produces are decomposed and change into acetic acid and hydrogen, also form carbonic acid gas when the most of organic acid of degraded.
Phase III is for producing methane phase.Methane-producing bacteria is converted into methane with acetic acid, acetate, carbonic acid gas and hydrogen etc.
Hypoxia device 550 is communicated with anaerobic device 540.Hypoxia device 550 is used for that coking chemical waste water is carried out biological denitrification to be processed.Hypoxia device 550 is anoxic pond or anoxic case.
Biological denitrification is processed and is referred to that under the environment of anoxic, facultative anaerobe is with the NO in water 3 -Or NO 2 -Replace oxygen as electron acceptor(EA), with NO 3 -Or NO 2 -Be reduced to oxynitride NO and the N of gaseous state by dissimilation 2Then O continues to be reduced to N 2Process.Denitrifying bacteria has heterotroph denitrifying bacteria and autotrophic type denitrifying bacteria and facultative chemosynthetic autotroph denitrifying bacteria.The heterotroph denitrifying bacteria under anaerobic utilizes NO 3 -Or NO 2 -In the oxygen deoxidation organic, obtain energy; Autotrophic type denitrifying bacteria such as thiobacillus denitrificans (T.denitrificans) utilize NO in anaerobic environment 3 -In oxygen sulphur or thiosulphate are oxidized to vitriol, therefrom obtain energy and assimilate CO 2Facultative chemosynthetic autotroph, the oxygenizement that can utilize hydrogen as Paracoccus denitrificans (Paracoccus denitrificans) is as the energy, with O 2Or NO 3 -As electron acceptor(EA), make NO 3 -Be reduced into N 2O or N 2
Aerobic device 560 is communicated with hypoxia device 550.Aerobic device 560 is used for allowing active sludge carry out aerobic repiration, further organic substance decomposing is become inorganics (such as water and carbonic acid gas).In present embodiment, aerobic device 560 is the multitube inner loop three phase fluidized bed reactor.Need to prove, aerobic device 560 also can be the three-phase fluidized bed of other types.
The multitube inner loop three phase fluidized bed reactor is a kind of novel fluidized-bed reactor, it is keeping tradition three-phase biologic fluidized-bed institute to have advantage: good mixing property in reactor, rate of mass transfer is fast, sludge concentration is large, organic loading high in, solved the problem of traditional three-phase biologic fluidized-bed existence, and have a series of new characteristics, be in particular in following:
1. can control the excessive increase of biofilm thickness.In tradition was three-phase biologic fluidized-bed, gas speed and liquid speed all can not be very large, if surpass widely the final Sedimentation Velocity of carrier, because carrier is only done the motion of unidirectional upper reaches, biomone will enter depositing separation area in a large number, therefore very easily take reactor out of.In order to prevent the loss of carrier, the shearing force of reactor inner fluid can not be controlled the microbial film of excessive increase effectively.And in circulating fluid bed, due to gas, liquid, solid in the up-flow district with fall between stream district and circulate, speed of circulation is very large, carrier but is difficult for being taken out of reactor, in the ordinary course of things, cycle rate is much larger than the heavy speed of EM, and the shearing action that fluid causes can effectively be controlled biofilm thickness, to avoid the inner transmission matter resistance that blocked up microbial film causes to increase, make circulating fluid bed middle microbial film keep higher activity.
2. the carrier current vector is few.Because circulating fluid bed turbulent fluctuation shearing and friction can make blocked up microbial film self falling, therefore can prevent a large amount of losses of carrier.
3. the carrier fluidizing performance is good.Tradition is three-phase biologic fluidized-bed for guaranteeing the abundant fluidisation of carrier, must adopt larger aspect ratio in the situation that do not reflux, the diameter that is reactor must be little, highly larger, and as long as the circulating biological fluidized-bed is up-flow cylinder diameter suitable (too small meeting cause bubble poly-and) and guarantee certain superficial gas velocity, just can realize that good carrier shunts.Simultaneously, carrier is in the up-flow district and fall between stream district and circulate, suffered friction, shearing force is basic identical, do not have the carrier demixing phenomenon in traditional three-phase fluidized bed, the carrier fluidisation has good homogeneity, and this is very favourable for biomembranous good growth.
4. the transfer efficiency of oxygen is high.The tradition three-phase fluidized bed all overflows from reactor head, and in circulating fluid bed, liquid is at upspout and fall stream and circulate between pipe, circulating liquid is carried under one's arms some small bubbles in upspout to enter and is fallen the stream pipe, only have portion gas to overflow from the top, gas-liquid contact time is extended, therefore oxygen-transfer efficiency is high.
Inner loop three phase fluidized bed reactor also has the following advantages: catalytic oxidation COD holding capacity is high relatively, can not suppress because influent COD is too high biochemical; Resistance to flow is little, can reduce in the situation that keep same speed of circulation air demand, thereby reduce working cost; The initial fluidisation of reactor is easier to, and has reduced the complicacy of operation operation; Because structure is compacter, can reduces institute and take up space and ground.
Secondary electrocatalysis oxidation apparatus 570 is communicated with aerobic device 560.Secondary electrocatalysis oxidation apparatus 570 is used for coking chemical waste water is carried out degree of depth electrooxidation, does not decompose larger molecular organics completely in flow process before further decomposing.Specifically in the present embodiment, secondary electrocatalysis oxidation apparatus 570 is the catalytic oxidation tower.
The oxygenant that uses in secondary electrocatalysis oxidation apparatus 570 is H 2SO 4And H 2O 2
Two-stage precipitation device 580 is communicated with secondary electrocatalysis oxidation apparatus 570.Two-stage precipitation device 520 is for the precipitation of removing coking chemical waste water.Different according to demand, two-stage precipitation device 580 can be the various ways such as settling tower, settling tank, settler.
BAF 610 is communicated with two-stage precipitation device 580.BAF 610 belongs to a kind of of aerobic device, is used for allowing active sludge carry out aerobic repiration, further organic substance decomposing is become inorganics.
Preferably, time of stopping in BAF 610 of coking chemical waste water is 12 hours.
BAF (BAF) is a kind of New biological membrane method sewage treatment process, maximum-norm reaches the hundreds of thousands of tpd, and develop into can denitrogenation dephosphorizing, has to remove SS, COD, BOD, nitrated, denitrogenation, dephosphorization, removal AOX(objectionable impurities) effect.BAF 610 collection bio-oxidations and hold back the suspended solids one have been saved post precipitation pond (second pond), have volumetric loading, hydraulic load is large, hydraulic detention time is short, required initial cost is few, and effluent quality is good: operation energy consumption is low, the characteristics that working cost is few.
Membrane bioreactor 620 is communicated with BAF 610.Membrane bioreactor 620 belongs to a kind of of aerobic device, is used for allowing active sludge carry out aerobic repiration, further organic substance decomposing is become inorganics.Membrane bioreactor 620 coordinates with aerobic device 560, and after processing, the water quality of water outlet is good.
Membrane bioreactor 620(MBR), as the reuse water treatment process.Due to the crown_interception of MBR, avoided the loss of microorganism, can keep high sludge concentration in bio-reactor, thereby improve volume load, reduced sludge loading, have extremely strong impact resistance.Again due to the crown_interception of film, SRT is extended, built and be conducive to breed microorganism growth slowly, as the environment of nitrobacteria growth, can improve the nitrification ability of system, be conducive to simultaneously improve the processing efficiency of difficult degradation larger molecular organics and impel it to decompose thoroughly.In operational process, larger Hydraulic Circulation is conducive to the even mixing of sewage, thereby makes active sludge that good dispersiveness be arranged, and has greatly improved processing efficiency and stability.
Coking chemical waste water oxidation and biochemical processing device 500 comprehensive utilization catalytic oxidation and bio-oxidation technology, the effectively organism in treatment of Coking Wastewater.
Further, coking wastewater processing system 10 also comprises sludge treatment device 900.Sludge treatment device 900 comprises sludge sump 910 and pressure filter 920.The precipitation that air-floating apparatus 130, one-level settler 520, hypoxia device 550, aerobic device 560, two-stage precipitation device 580, BAF 610 and membrane bioreactor 620 produce is sent into sludge sump 910.After the mud of sludge sump 910 adds the pressure filter press filtration via pneumatic diaphragm pump, the mud outward transport, the filtrate re-injection enters setting device 120.
Coking wastewater deep treatment equipment 700 comprises one-level rough filtering device 710, secondary rough filtering device 720, one-level transition apparatus 730, one-level security personnel filtration unit 740, nanofiltration device 750, secondary transition apparatus 760, secondary security personnel's filtration unit 770 and reverse-osmosis filtering device 780.
One-level rough filtering device 710 is communicated with membrane bioreactor 620.One-level rough filtering device 710 is used for the coking chemical waste water of processing through coking chemical waste water oxidation and biochemical processing device 500 is filtered, the fine suspension in filtered water, microorganism, part heavy metal ion etc., and can effectively reduce the colourity of water.
Preferably, one-level rough filtering device 710 is the filtration apparatus of tank type, and shell is generally carbon steel, stainless steel or glass reinforced plastic, the inner filtrate of filling.
Preferably, the filtrate of one-level rough filtering device 710 is selected from least a in zeolite and glaukonine.Be preferably zeolite.Zeolite is a kind of polar material, is the very strong sorbent material of polarity, to polar molecule and unsaturated molecule organism, as halohydrocarbon, very strong adsorption effect is arranged, and the large molecule of polarizability in non-polar molecule is also had higher selection absorption advantage.Zeolite filler mainly comprises using natural clinoptilolite filtrate and active zeolite filtrate.
Secondary rough filtering device 720 is communicated with one-level rough filtering device 710.Secondary rough filtering device 720 is used for removing coking chemical waste water fine suspension, microorganism, part heavy metal ion etc., and can effectively reduce the colourity of water.
Secondary rough filtering device 720 is the filtration apparatus of tank type, and shell is generally carbon steel, stainless steel or glass reinforced plastic, the inner filtrate of filling.
Preferably, the filtrate of secondary rough filtering device 720 is selected from least a in gac and bamboo charcoal, is preferably gac.Carbon leaching material has flourishing central hole structure and flourishing specific surface area, and loading capacity is large, filtration velocity is fast, does not contain the characteristic of zinc salt, is a kind of good filtrate.
One-level transition apparatus 730 is communicated with secondary rough filtering device 720.One-level transition apparatus 730 is used for accommodating the coking chemical waste water of processing through secondary rough filtering device 720, keeps the turnover of whole system current stable, plays shock absorption.One-level transition apparatus 730 can be transition pond or transition case.Need to prove, one-level transition apparatus 730 also can be arranged between one-level rough filtering device 710 and secondary rough filtering device 720, be that one-level transition apparatus 730 is communicated with one-level coarse filtration filter device 710 and secondary rough filtering device 720, after coking chemical waste water after one-level rough filtering device 710 filters enters one-level transition apparatus 730, then enter secondary rough filtering device 720 and carry out the secondary coarse filtration.
One-level security personnel filtration unit 740 is communicated with one-level transition apparatus 730.Security personnel filter in the process of (cartridge filtration), and water enters filter core inside from the outside of microstraining core, and trace suspension thing or fine impurities particulate matter are trapped within the process of filter core outside.One-level security personnel filtration unit 740 is used for removing by filter the above impurity of 50 μ m.The filtrate of one-level security personnel filtration unit 740 is polypropylene, and the space is 1 μ m ~ 300 μ m, adopts close outer thin structure in five interior axles.One-level security personnel filtration unit 740 is provided with for the dispensing mouth of throwing in Scale inhibitors.
Nanofiltration device 750 is communicated with one-level security personnel filtration unit 740.Nanofiltration (NF) is a kind of membrane separation technique between ultrafiltration and reverse osmosis, and its molecular weight cut-off is in the scope of 80-1000, and the aperture is several nanometers.After filtering through the senior filtration unit such as nanofiltration, have about 70% water to become the water of water quality reaching standard, these water are outer defeated, and the water of residue 30% is along with filtering increasing continuously of the water yield, and the composition of the inside (pollutent) is accumulation constantly, is dense water.The dense water re-injection that obtains after nanofiltration device 750 is filtered is to setting device 120.
Secondary transition apparatus 760 is communicated with nanofiltration device 750.Secondary transition apparatus 760 is used for accommodating the coking chemical waste water of processing through nanofiltration device 750.Secondary transition apparatus 760 can be transition pond or transition case.
Secondary security personnel filtration unit 770 is communicated with secondary transition apparatus 760.The filtrate of secondary security personnel filtration unit 770 is polypropylene, and the space is 1 μ m ~ 300 μ m, adopts close outer thin structure in five interior axles.Secondary security personnel filtration unit 770 is provided with for the dispensing mouth of throwing in Scale inhibitors.
Reverse-osmosis filtering device 780 is communicated with secondary security personnel filtration unit 770.
Reverse osmosis (RO) technology is a kind of advanced person's membrane separation technique.This technology makes that in the solution that wish separates, some composition under the effect of pressure, sees through a kind of semi-permeable membranes-reverse osmosis membrane of selecting perviousness that has, and collect in the low-tension side of film and see through thing, be by the strong solution of other composition of detention in the high-tension side of film.It is a kind of energy-conservation, efficient, pollution-free and practical new and high technology.
Water enters a kind of solution by a kind of semi-permeable membranes or the natural flow from a kind of dilute solution to a kind of denseer solution is called infiltration.This water or solution are had select the film of perviousness to be referred to as semi-permeable membranes.But add on one side that in strong solution suitable pressure can make infiltration stop, the pressure when dilute solution stops to the infiltration of strong solution is called osmotic pressure.Reverse osmosis is to add on one side than naturally osmotic in strong solution to press higher pressure, and reverse the naturally osmotic direction, the other side of the hydraulic pressure in strong solution to semi-permeable membranes, this is opposite with natural normal process of osmosis, therefore is called reverse osmosis.This special semi-permeable membranes is called reverse osmosis membrane.
The major portion of reverse-osmosis filtering device 780 main frames is RO membrane modules.The RO film, i.e. reverse osmosis membrane, the aperture reaches 0.0001 micron, can filter 70% macromole, comprises salinity.The RO film that native system adopts can guarantee that the main frame desalination is long-term, stablize, reaches reliably design requirements, this reverse osmosis host design reverse osmosis water temperature is 25 ℃, and the utilization ratio of water is 70%, and the total ratio of desalinization of system is more than or equal to 97%, and the random display of specific conductivity is arranged, and with auto-alarm function.
See also Fig. 2, Figure 2 shows that RO processing technological flow figure.
Clear water after reverse-osmosis filtering device 780 filters flows in clean water basin 800, but Reuse on Environment or other process water; Dense water re-injection after filtration is to setting device 120.
Dense water after one-level rough filtering device 710, secondary rough filtering device 720, nanofiltration device 750 and reverse-osmosis filtering device 780 and backwashing water re-injection are to setting device 120.
The COD value of the coking chemical waste water of processing through coking wastewater deep advanced treatment device 700 is lower, and the while can be removed the impurity in coking chemical waste water, makes the coking chemical waste water can qualified discharge.
After coking chemical waste water process coking chemical waste water coal tar treatment facility 100, coking chemical waste water oxidation and biochemical processing device 500 and coking wastewater deep treatment equipment 700 are processed, can effectively remove suspended substance, organism and ammonia nitrogen in coking chemical waste water, the coking chemical waste water of the processing of final output can reach emission standard.The waste water of final output, pH value be 7 ~ 9, COD less than 500mg/L, suspended substance is less than 600mg/L, volatile phenol is less than 0.5mg/L, prussiate is less than 0.5mg/L, ammonia nitrogen is less than 25mg/L.
Need to prove, one-level transition apparatus 730 and secondary transition apparatus 760 can omit, and this moment, one-level security personnel filtration unit 740 directly was communicated with secondary rough filtering device 720, and secondary security personnel filtration unit 770 directly is communicated with nanofiltration device 750.
See also Fig. 1, the coking waste water treatment method of an embodiment comprises the following steps:
Step S101, provide coking wastewater processing system 10.
Step S102, the larger suspension oil of particle that uses oil-isolating device 110 to remove in coking chemical waste water.
Concrete, oily(waste)water enters in the pond that the plane is rectangle by distributing trough, the along continuous straight runs sluggish flow, and oils floats up to the water surface in flowing, and is pushed to by oil header or the Oil scraper that is arranged on the pond face and then flows into water knockout in oil header.The heavy oil that precipitates in the pond and other impurity accumulate in the pool bottom sludge bucket, enter in sludge tank by shore pipe, and the waste water of processing through oil removal overflow enters discharge channel and discharges outside the pond, carries out subsequent disposal, to remove oil in water emulsion and other pollutents.
Preferably, coking chemical waste water stopped in oil-isolating device 110 2 hours ~ 6 hours.
Need to prove, coking chemical waste water can use equalizing tank or surge tank (not shown) to process before entering oil-isolating device 110 processing, the waste water that enters oil-isolating device 110 is homogenized, it is stable that thereby assurance enters the water quality of the coking chemical waste water of oil-isolating device 110, therefore, equalizing tank or surge tank can be set before oil-isolating device 110.In present embodiment, the volume ratio of equalizing tank or surge tank and oil-isolating device 110 is 1:5 ~ 1:3.
Preferably, use setting device to process the coking chemical waste water of processing through oil-isolating device 110, the coking chemical waste water of processing through oil-isolating device 110 is homogenized.
Step S103, use air-floating apparatus 130 are removed suspended substance larger in coking chemical waste water.
Air supporting is to utilize the micro-bubble of high dispersing to remove to adhere to the object of hydrophobic group in waste water for carrier, its small bubbles and object is looked as a whole, and its global density floats to the water surface on less than water, thereby realizes the process that solid-liquid or liquid liquid separate.Air-floating apparatus 130 can for horizontal flow air flotation device or flow lifting type air-floating apparatus, be preferably horizontal flow air flotation device.
The principle that produces according to microbubble is different, air-floating apparatus 130 can be aeration air-floating apparatus, dissolved air flotation device and electrofloatation device, as long as can remove the larger suspended substance in coking chemical waste water, also at least two in aeration air-floating apparatus, dissolved air flotation device and electrofloatation device series connection can be used as required.
Air-dissolving air-float refers to that air pressurized is dissolved in water and reaches capacity, and the decompression of dissolved air water stream disengages microbubble when entering air flotation pool.Pressure air-dissolving water can be all or part of of the water of processing, can be also the recirculation water of air flotation pool water outlet, and the per-cent that the backflow water yield accounts for the water yield of processing claims reflux ratio, is the important factor that affects daf efficiency, must be determined by test.The equipment of pressure air-dissolving method has force (forcing) pump, dissolving and air compressor etc.Dissolving is the pressure-bearing steel cylinder, inner standing flow deflector or the placement filler put.The dissolving water outlet enters air flotation pool by reducing valve or reliever.
Preferably, throw in emulsion splitter at the reaction zone of air-floating apparatus 130, it is 7% aluminum chloride that emulsion splitter is preferably concentration, certainly, other in the industry emulsion splitters commonly used also can.Specifically in the process of operation, determine the injected volume of emulsion splitter according to the content of coal tar in the coking chemical waste water that enters air-floating apparatus 130, when in coking chemical waste water, oleaginousness is in 400mg/L, the injected volume of emulsion splitter is the amount of 500mg/L(emulsion splitter and the volume ratio of coking chemical waste water), when oleaginousness was 400mg/L ~ 1000mg/L, the emulsion splitter injected volume was 400mg/L ~ 1000mg/L.
Preferably, the time of air-floating apparatus 130 Treatment of Wastewater in Coking is 0.5 hour ~ 2 hours.
Preferably, the oleaginousness of the coking chemical waste water of process air-floating apparatus 130 processing is in 30mg/L.
Preferably, through setting device 120 regulate the coking chemical waste water that homogenizes first used before entering air-floating apparatus 130 stripping tower 300 remove coking chemical waste water in ammonium ion (NH 4+) and free ammonia (NH 3) the nitrogen that exists of form.The coking chemical waste water that process stripping tower 300 is processed again enters to regulate in setting device 120 and homogenizes, and then uses air-floating apparatus to remove larger suspended substance in coking chemical waste water.
Step S104, the emulsification shape coal tar that uses acid out device 140 further to remove in coking chemical waste water.
The coking chemical waste water of discharging from air-floating apparatus 130 enters acid out device 140, adds sulfuric acid to do acid out and processes the emulsification shape coal tar of further removing in coking chemical waste water.
Preferably, the injected volume of sulfuric acid is 50mg/L.Sulfuric acid can have two kinds of addition meanss, and the first 98% vitriol oil directly adds, and this sink drainage contains aeration, whipping appts, can mix; Its two, the sulphuric acid soln of the diluting concentrated sulfuric acid to 10% with 98% ~ 20% concentration.
After coking chemical waste water is processed through step S101 ~ step S104, the content of coal tar in 20mg/L, can be avoided coal tar excessive in coking chemical waste water that follow-up treatment facility is produced and destroy.
Step S105, use 510 pairs of coking chemical waste waters of one-level electrocatalysis oxidation apparatus to carry out catalytic oxidation, with improve in coking chemical waste water 5 days biochemical oxygen demand (BOD) (BOD5) with the ratio of chemical oxygen demand (COD) (COD).
Preferably, time of stopping in one-level electrocatalysis oxidation apparatus 510 of coking chemical waste water is 40 minutes ~ 90 minutes.
Concrete, under acidic conditions, in 6~24V of catalytic oxidation low dc voltage electrostatic field, have under the condition of catalyzer existence, after regulating pH≤4, when catalytic oxidation is processed, catalyzer is FeSO 4And H 2O 2
In this step, add FeSO under acidic conditions 4And H 2O 2Generate simultaneously the sub-OH of hydroxyl radical free radical, because OH has extremely strong oxidisability, make partial organic substances become CO2 and H2O, remaining organism is hydrolyzed-acidifying, and the sub-chain rupture of macromole becomes small molecules, further makes small organic molecule be oxidized to organic acid, thereby promote BOD5/COD ratio, established the basis of follow-up biochemical treatment.Subsequent treatment process " hydrolysis " and " acidifying " effect by anerobe, and follow-up aerobic bacteria digests, the organism after the anaerobism are resolved into CO by the aerobic bacteria absorption as nutriment 2And H 2O。
Step S106, the precipitation of using one-level settler 520 to remove in coking chemical waste water.
Concrete, adopt the settling tower with sludge bucket, enter with the sewage of suspended substance and standingly complete precipitation process after to sedimentation of suspension to sludge bucket afterwards.
Different according to demand, one-level settler 520 can be the various ways such as settling tower, settling tank, settler.
Step S107, the pH value of using transition apparatus 530 to regulate coking chemical waste water.
In present embodiment, the pH value to 6.5 of using sodium hydroxide solution to regulate to be housed in the coking chemical waste water in transition apparatus 530 ~ 7.5.Preferably, the mass concentration of sodium hydroxide solution is 7%.Need to prove, the pH value that is housed in transition apparatus 530 is not limited to be adjusted to 6.5 ~ 7.5, regulates according to the requirement of subsequent disposal the pH value that is housed in the coking chemical waste water in transition apparatus 530.Simultaneously, also be not limited to use sodium hydroxide solution to regulate the pH value of coking chemical waste water, use other basic solutions such as potassium hydroxide, sodium carbonate etc. or the alkaline waste water can.
Step S108,540 pairs of coking chemical waste waters of use anaerobic device carry out anaerobic biological treatment.
Coking chemical waste water is carried out anaerobic biological treatment, thereby the organic substance decomposing in coking chemical waste water is converted into inorganics.Preferably, coking chemical waste water stopped in anaerobic device 540 6 hours ~ 12 hours.
Anaerobic waste water biological treatment refers under condition of free-dioxygen the various complicated organic substance decomposing in waste water to be changed into the process of the materials such as methane and carbon dioxide by the anaerobion effect of (comprising facultative microbe), also claims anaerobic digestion.The fundamental difference of anaerobic waste water biological treatment and aerobic processes is not with molecular oxygen as hydrogen acceptor, and take combined oxygen, carbon, sulphur, nitrogen etc. as hydrogen acceptor.
Anaerobic biological treatment is the chemistry of micro-organisms process of a complexity, relies on the bacterium of three large main monoids, and the combined action that namely is hydrolyzed acid formers, hydrogen-producing acetogenic bacteria and methane-producing bacteria is completed.Thereby roughly anaerobic digestion process is divided into three continuous stages, namely acidication stage, product hydrogen produce the acetic acid stage and produce methane phase.
Fs is the acidication stage.Complicated macromole, insoluble organism first are hydrolyzed to small molecules, dissolved organic matter under the effect of perienzyme, then infiltrate in cell paste, be decomposed into small molecules, dissolved organic matter, then infiltrate in cell paste, decompose generation VFA, alcohols, aldehydes etc.This stage mainly produces than higher fatty acid.
Subordinate phase is produced the acetic acid stage for producing hydrogen.Under the effect of hydrogen-producing acetogenic bacteria, the various organic acids that the fs produces are decomposed and change into acetic acid and hydrogen, also form carbonic acid gas when the most of organic acid of degraded.
Phase III is for producing methane phase.Methane-producing bacteria is converted into methane with acetic acid, acetate, carbonic acid gas and hydrogen etc.
Step S109,550 pairs of coking chemical waste waters of use hypoxia device carry out biological denitrification to be processed.
Preferably, coking chemical waste water stopped in hypoxia device 550 6 hours ~ 12 hours.
Biological denitrification is processed and is referred to that under the environment of anoxic, facultative anaerobe is with the NO in water 3 -Or NO 2 -Replace oxygen as electron acceptor(EA), with NO 3 -Or NO 2 -Be reduced to oxynitride NO and the N of gaseous state by dissimilation 2Then O continues to be reduced to N 2Process.Denitrifying bacteria has heterotroph denitrifying bacteria and autotrophic type denitrifying bacteria and facultative chemosynthetic autotroph denitrifying bacteria.The heterotroph denitrifying bacteria under anaerobic utilizes NO 3 -Or NO 2 -In the oxygen deoxidation organic, obtain energy; Autotrophic type denitrifying bacteria such as thiobacillus denitrificans (T.denitrificans) utilize NO in anaerobic environment 3 -In oxygen sulphur or thiosulphate are oxidized to vitriol, therefrom obtain energy and assimilate CO 2Facultative chemosynthetic autotroph, the oxygenizement that can utilize hydrogen as Paracoccus denitrificans (Paracoccus denitrificans) is as the energy, with O 2Or NO 3 -As electron acceptor(EA), make NO 3 -Be reduced into N 2O or N 2
Step S110,560 pairs of coking chemical waste waters of the aerobic device of use carry out aerobic treatment.
In this step, add active sludge in aerobic device 560, generally obtain from domestic sewage factory, the strong aeration of active sludge makes dissolved oxygen more than 2mg/L.
Preferably, time of stopping in aerobic device 560 of coking chemical waste water is 12 hours ~ 36 hours.
Step S111,570 pairs of coking chemical waste waters of use secondary electrocatalysis oxidation apparatus carry out degree of depth catalytic oxidation to be processed.
Preferably, coking chemical waste water carries out before degree of depth catalytic oxidation processes, and first uses sulfuric acid to be adjusted to 3.5 ~ 4.5 through the pH value of the coking chemical waste water of aerobic device 560 processing.Specifically in the present embodiment, the mass concentration of sulfuric acid is 5%.
Preferably, using 570 pairs of coking chemical waste waters of secondary electrocatalysis oxidation apparatus to carry out degree of depth catalytic oxidation processes the catalyzer that uses and is H 2SO 4And H 2O 2
Preferably, time of stopping in secondary electrocatalysis oxidation apparatus 570 of coking chemical waste water is 45 minutes.
Step S112, the precipitation of using two-stage precipitation device 580 to remove in coking chemical waste water.
Different according to demand, two-stage precipitation device 580 can be the various ways such as settling tower, settling tank, settler.
Preferably, add sodium hydroxide in this step in coking chemical waste water.
Step S113,610 pairs of coking chemical waste waters of use BAF are processed.
Preferably, time of stopping in BAF 610 of coking chemical waste water is 12 hours.
Step S114,620 pairs of coking chemical waste waters of use membrane bioreactor are processed.
Preferably, in the coking chemical waste water through step S101 ~ 114 processing, COD is down in 500mg/L, and volatile phenol is in 0.5mg/L, and oil-containing is in 20mg/L, and suspended solid is in 20mg/L.
Step S115,710 pairs of coking chemical waste waters of use one-level rough filtering device carry out the one-level coarse filtration.
The one-level coarse filtration is used for fine suspension, microorganism, part heavy metal ion in filtered water etc., and can effectively reduce the colourity of water.
Step S116,720 pairs of coking chemical waste waters of use secondary rough filtering device carry out the secondary coarse filtration.
Step S117,740 pairs of coking chemical waste waters of use one-level security personnel's filtration unit carry out the one-level security personnel and filter.
The one-level security personnel filter and are used for removing the above impurity of coking chemical waste water 50 μ m.
Preferably, carry out to add Scale inhibitors in one-level is ensured public security filtration unit 740 in the process of one-level security personnel filtration.
Preferably, also comprise step between step S116 and step S117: will inject First Transition device 730 through the coking chemical waste water of secondary coarse filtration.
Step S118,750 pairs of coking chemical waste waters of use nanofiltration device carry out nanofiltration.
Coking chemical waste water is carried out the impurity that nanofiltration is used for removing coking chemical waste water 1nm ~ 10nm.
Step S119,770 pairs of coking chemical waste waters of use secondary protective device carry out the secondary security personnel and filter.
Preferably, carry out to add Scale inhibitors in secondary is ensured public security filtration unit 770 in the process of secondary security personnel filtration.
Preferably, also comprise step between step S118 and step S119: will inject the second transition apparatus 760 through the coking chemical waste water of nanofiltration.
Step S120, use reverse-osmosis filtering device 780 devices carry out osmosis filtration to coking chemical waste water and process.
The coking chemical waste water of processing through osmosis filtration flows in clean water basin 800, can be used for greening or other process water; Dense water re-injection after filtration is to setting device 120.
Preferably, the dense water that obtains after step S115, step S116, step S118 and step S120 process and backwashing water re-injection are to setting device 120.
Preferably, the precipitation of step S103, step S106, step S109, step S110, step S112, step S113 and step S114 generation is sent into sludge sump 910.The mud of sludge sump 910 is after the pressure filter press filtration, and mud is transported outward, and the filtrate re-injection enters setting device 120.
After the above-mentioned coking waste water treatment method of coking chemical waste water is processed, can effectively remove suspended substance, organism and ammonia nitrogen in coking chemical waste water, the coking chemical waste water of the processing of final output can reach emission standard.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.Should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (10)

1. a coking wastewater processing system, is characterized in that, comprising:
Coking chemical waste water coal tar treatment facility, the coal tar for removing coking chemical waste water comprises:
Oil-isolating device is used for removing the larger suspension oil of coking chemical waste water particle;
Air-floating apparatus is communicated with described oil-isolating device, and described air-floating apparatus is used for removing the larger suspended substance of coking chemical waste water; And
The acid out device is communicated with described air-floating apparatus, and described acid out device is used for further removing the coal tar of coking chemical waste water;
Coking chemical waste water oxidation and biochemical processing device comprise:
The one-level electrocatalysis oxidation apparatus is communicated with described acid out device, and described one-level electrocatalysis oxidation apparatus is used for coking chemical waste water is carried out catalytic oxidation;
The one-level settler is communicated with described one-level electrocatalysis oxidation apparatus, and described one-level settler is for the precipitation of removing coking chemical waste water;
Transition apparatus is communicated with described one-level settler, and described transition apparatus is used for accommodating the coking chemical waste water of processing through described one-level settler;
Anaerobic device is communicated with described transition apparatus, and described anaerobic device is used for coking chemical waste water is carried out anaerobic biological treatment;
Hypoxia device is communicated with described anaerobic device, and described hypoxia device is used for that described coking chemical waste water is carried out biological denitrification to be processed;
Aerobic device is communicated with described hypoxia device, and described aerobic device is used for described coking chemical waste water is carried out aerobic treatment;
The secondary electrocatalysis oxidation apparatus is communicated with described aerobic device, and described secondary electrocatalysis oxidation apparatus is used for that coking chemical waste water is carried out degree of depth catalytic oxidation to be processed;
The two-stage precipitation device is communicated with described secondary electrocatalysis oxidation apparatus, and described two-stage precipitation device is for the precipitation of removing coking chemical waste water;
BAF is communicated with described two-stage precipitation device; And
Membrane bioreactor is communicated with described BAF;
Coking wastewater deep treatment equipment is used for coking chemical waste water is carried out advanced treatment, comprising:
The one-level rough filtering device is communicated with described membrane bioreactor, and described one-level rough filtering device is used for described coking chemical waste water is carried out the one-level coarse filtration;
The secondary rough filtering device is communicated with described one-level rough filtering device, and described secondary rough filtering device is used for described coking chemical waste water is carried out the secondary coarse filtration;
One-level security personnel filtration unit is communicated with described secondary rough filtering device, and described one-level security personnel filtration unit is used for that coking chemical waste water is carried out the one-level security personnel and filters;
Nanofiltration device is communicated with described one-level security personnel filtration unit, and described nanofiltration device is used for that coking chemical waste water is carried out nanofiltration and processes;
Secondary security personnel filtration unit is communicated with described nanofiltration device, and described secondary security personnel filtration unit is used for that coking chemical waste water is carried out the secondary security personnel and filters; And
Reverse-osmosis filtering device is communicated with described secondary security personnel filtration unit, and described reverse-osmosis filtering device is used for coking chemical waste water is carried out osmosis filtration.
2. coking wastewater processing system according to claim 1, it is characterized in that, described coking wastewater processing system also comprises the stripping tower that is communicated with the setting device of coking chemical waste water coal tar treatment facility, and described stripping tower is used for removing the nitrogen that coking chemical waste water exists with ammonium ion and free ammonia state.
3. coking wastewater processing system according to claim 1, it is characterized in that, described coking wastewater processing system also comprises sludge treatment device, described sludge treatment device comprises sludge sump and pressure filter, described sludge sump is used for accommodating the precipitation that described air-floating apparatus, described one-level settler, described hypoxia device, described aerobic device, described two-stage precipitation device, described BAF and described membrane bioreactor produce, and the mud that described pressure filter is used for described sludge sump is accommodated carries out press filtration.
4. the coking waste water treatment method of right to use requirement 1 ~ 3 described coking wastewater processing system of any one, is characterized in that, comprises the following steps:
Use the larger suspension oil of particle in oil-isolating device removal coking chemical waste water;
Use air-floating apparatus to remove suspended substance larger in coking chemical waste water;
Use acid out device is further removed the emulsification shape coal tar in coking chemical waste water;
Use the one-level electrocatalysis oxidation apparatus to carry out catalytic oxidation to coking chemical waste water;
Use one-level settler is removed the precipitation in coking chemical waste water;
Use transition apparatus to regulate the pH value of coking chemical waste water;
Use anaerobic device to carry out anaerobic biological treatment to coking chemical waste water;
Using hypoxia device to carry out biological denitrification to coking chemical waste water processes;
Use aerobic device to carry out aerobic treatment to coking chemical waste water;
Using the secondary electrocatalysis oxidation apparatus to carry out degree of depth catalytic oxidation to coking chemical waste water processes;
Use two-stage precipitation device is removed the precipitation in coking chemical waste water;
Use BAF that coking chemical waste water is processed;
Use membrane bioreactor that coking chemical waste water is processed;
Use the one-level rough filtering device to carry out the one-level coarse filtration to coking chemical waste water;
Use the secondary rough filtering device to carry out the secondary coarse filtration to coking chemical waste water;
Using one-level security personnel filtration unit to carry out the one-level security personnel to coking chemical waste water filters;
Use nanofiltration device to carry out nanofiltration to coking chemical waste water;
Using the secondary protective device to carry out the secondary security personnel to coking chemical waste water filters; And
Using reverse-osmosis filtering device to carry out osmosis filtration to coking chemical waste water processes.
5. coking waste water treatment method according to claim 4, it is characterized in that, also comprise step after the step of the suspension oil that the particle in described use oil-isolating device removal coking chemical waste water is larger: use setting device to process the coking chemical waste water of process oil-isolating device processing, the coking chemical waste water that enters described air-floating apparatus is homogenized.
6. coking waste water treatment method according to claim 5, it is characterized in that, also comprise step in described use air-floating apparatus is removed coking chemical waste water before the step of larger suspended substance: the nitrogen that will use through the coking chemical waste water that homogenizes that setting device is processed stripping tower to exist with the form of ammonium ion and free ammonia in removing coking chemical waste water enters described air-floating apparatus after the coking chemical waste water of processing through stripping tower is processed through setting device again.
7. coking waste water treatment method according to claim 4, it is characterized in that, also comprise step described use secondary rough filtering device carries out the step of secondary coarse filtration to coking chemical waste water after: the coking chemical waste water that will advance the secondary coarse filtration injects the First Transition device, and the coking chemical waste water of processing through the First Transition device re-uses described one-level security personnel filtration unit to carry out the one-level security personnel and filter.
8. coking waste water treatment method according to claim 4, it is characterized in that, carrying out the step of nanofiltration to coking chemical waste water after, described use nanofiltration device also comprises step, to inject the second transition apparatus through the coking chemical waste water of nanofiltration, the coking chemical waste water of processing through the second transition apparatus re-uses described secondary security personnel filtration unit to carry out the secondary security personnel and filters.
9. coking waste water treatment method according to claim 4, is characterized in that, uses described one-level electrocatalysis oxidation apparatus that coking chemical waste water is carried out adding FeSO when catalytic oxidation is processed under acidic conditions 4And H 2O 2Carry out catalytic oxidation.
10. coking waste water treatment method according to claim 4, is characterized in that, uses described secondary electrocatalysis oxidation apparatus to be H to the oxygenant that coking chemical waste water carries out using when degree of depth catalytic oxidation is processed 2SO 4And H 2O 2
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