CN203173900U - Coking waste water deep treatment equipment - Google Patents
Coking waste water deep treatment equipment Download PDFInfo
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- CN203173900U CN203173900U CN 201320042812 CN201320042812U CN203173900U CN 203173900 U CN203173900 U CN 203173900U CN 201320042812 CN201320042812 CN 201320042812 CN 201320042812 U CN201320042812 U CN 201320042812U CN 203173900 U CN203173900 U CN 203173900U
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Abstract
Coking waste water deep treatment equipment comprises a primary rough filtration device, a secondary rough filtration device, a primary safety protection filtration device, a nanofiltration device, a secondary safety filtration device and an inverse penetration filtration device, wherein the primary rough filtration device is used for carrying out primary rough fitler of coking waste water; the primary rough filtration device is communicated with the primary rough filtration device and used for carrying out secondary rough filtration of the coking waste water; the primary safety protection filtration device is communicated with the secondary rough filtration device and used for carrying out primary safety protection filtration of the coking waster water; the nanofiltration device is communicated with the primary safety protection filtration device and used for carrying out nonofiltration treatment of the coking waste water; the secondary safety protection filtration device is communicated with the nanofiltration device and used for carrying out secondary safety protection filtration of the coking waste water; the inverse penetration filtration device is communicated with the secondary safety protection filtration device and used for carrying out inverse penetration filtration of the coking waste water. The coking waste water deep treatment equipment has better treatment effect.
Description
Technical field
The utility model relates to a kind of coking wastewater deep treatment equipment.
Background technology
Coking chemical waste water has comprised the waste water that produces in gas production, coking, metallurgy and the pottery cellar for storing things stove production process, has had high organism, high phenol, high ammonia nitrogen characteristics, even have also contain cyanogen, suspended substance and colourity are also very high, belong to the organic waste water of high density bio-refractory.COD value through the coking chemical waste water of peroxidation and biochemical treatment is still higher, can not directly discharge, and needs to use coking wastewater deep treatment equipment to handle.The treatment effect of existing coking wastewater deep treatment equipment is relatively poor.
The utility model content
Based on this, be necessary to provide a kind for the treatment of effect coking wastewater deep treatment equipment preferably.
A kind of coking wastewater deep treatment equipment is used for coking chemical waste water is carried out advanced treatment, comprising:
One-level rough filtering device, described one-level rough filtering device are 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 handles;
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.
Therein among embodiment, the filtration apparatus that described one-level rough filtering device is the tank body formula.
Therein among embodiment, the filtration apparatus that described secondary rough filtering device is the tank body formula.
Among embodiment, also comprise the one-level transition apparatus therein, described one-level transition apparatus is communicated with described one-level rough filtering device and secondary rough filtering device.
Among embodiment, also comprise the secondary transition apparatus therein, described secondary transition apparatus is communicated with described nanofiltration device and described secondary security personnel filtration unit.
Among embodiment, described one-level security personnel filtration unit is provided with for the dispensing mouth of throwing in Scale inhibitors therein.
Among embodiment, described secondary security personnel filtration unit is provided with for the dispensing mouth of throwing in Scale inhibitors therein.
The COD value of the coking chemical waste water of above-mentioned coking wastewater deep treatment device processes is lower, can remove simultaneously the impurity in the 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 synoptic diagram of osmosis filtration treatment process.
Embodiment
For the ease of understanding the utility model, with reference to relevant drawings the utility model is described more fully below.Provided first-selected embodiment of the present utility model in the accompanying drawing.But the utility model can be realized with many different forms, be not limited to embodiment described herein.On the contrary, providing the purpose of these embodiment is to make to disclosure of the present utility model more thoroughly comprehensively.
Need to prove that 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 to be directly connected to another element or may to have element placed in the middle simultaneously.Term as used herein " vertical ", " level ", " left side ", " right side " and similar statement are just for illustrative purposes.
Unless otherwise defined, the employed all technology of this paper are identical with the implication that belongs to those skilled in the art's common sense of the present utility model with scientific terminology.Employed term is not intended to be restriction the utility model just in order to describe the purpose of specific embodiment in specification sheets of the present utility model herein.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 removal device 110, setting device 120, air-floating apparatus 130 and acid out device 140.
The structure of oil removal 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 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 flows into water knockout in the oil header then.The heavy oil that precipitates in the pond and other impurity accumulate in the pool bottom sludge bucket, enter in the sludge tank by shore pipe, and the waste water that the process oil removal is handled then overflow is gone into outside the discharge channel discharge 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 handle before entering 110 processing of oil removal device, the waste water that enters oil removal device 110 is homogenized, it is stable that thereby assurance enters the water quality of the coking chemical waste water of oil removal device 110, therefore, equalizing tank or surge tank can be set before oil removal device 110.In the present embodiment, the volume ratio of equalizing tank or surge tank and oil removal device 110 is 1:5 ~ 1:3.
Air-floating apparatus 130 is connected with setting device 120.Air-floating apparatus 130 is used for removing the bigger 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 the waste water for carrier, and its small bubbles and object are looked as a whole, and its global density floats to the water surface on less than water, thereby realizes solid-liquid or liquid liquid separating process.Air-floating apparatus 130 can be preferably the flat flow air-floating apparatus for flat flow air-floating apparatus or flow lifting type air-floating apparatus.
Principle difference according to the microbubble generation, air-floating apparatus 130 can be aeration air-floating apparatus, dissolved air flotation device and electrofloatation device, as long as can remove the bigger suspended substance in the 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 the water and reaches capacity that 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 handling, also can be the recirculation water of air flotation pool water outlet, and the per-cent that the backflow water yield accounts for the water yield of handling claims reflux ratio, is the important factor that influences 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, separates (using precipitation or air supporting) then.In the present embodiment, acid out is with acid (hydrochloric acid or sulfuric acid) oil in water emulsion in the water to be become suspended matter.Need to prove that acid out can be acid out device independently, also can add the acid out function at equipment such as settling tower, air supportings, is exactly that a chemicals dosing plant that adds sour agent adds stirrer in fact.
The content of coal tar can be avoided excessive coal tar that follow-up treatment facility is produced and destroy in 20mg/L after coking chemical waste water was handled through coking chemical waste water coal tar treatment facility 100.
NH
4+And NH
3Equilibrium relationship as follows:
NH
3+H
2O→NH
4++OH
-
This equilibrium relationship is subjected to the influence 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 sides, and pH is when being 11 left and right sides, and free ammonia roughly accounts for 98%, and free ammonia is easy to overflow from water, as aeration in addition, then can impel ammonia to overflow from water, and wherein, pH is the effect key.
The rate of dissociation (%, the i.e. separation rate of free ammonia and water) of ammonia nitrogen is as shown in the table under different pH, the temperature
| 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 speaking, 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 the pH value is showered into from the top of tower on the 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, finish mass transfer process, make ammonia transfer gas phase to by liquid phase, with the air discharging, finish 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 then is everlasting and is carried out stripping under the warm-up mode.
Ammonia gas subsequent behind the stripping enters ammonia absorption cleaning tower, makes ammonia and absorption liquid produce chemical reaction in tower, can make gas qualified discharge, pollution-free.
Need to prove that setting device 120 can be omitted, oil removal this moment device 110 directly is communicated with air-floating apparatus 130, and the coking chemical waste water of handling by oil removal device 110 this moment directly enters in the air-floating apparatus 130 to be handled; Or oil removal device 110 is communicated with stripping tower 300, stripping tower 300 is communicated with air-floating apparatus 130, the coking chemical waste water of handling by oil removal device 110 this moment enters in the stripping tower 300 to be handled, and the coking chemical waste water that process stripping tower 300 is handled enters air-floating apparatus 130 and handles.
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 the 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 the 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, behind adjusting pH≤4, add an amount of FeSO
4And H
2O
2, generate the sub-OH of hydroxyl radical free radical simultaneously, 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 is by " hydrolysis " and " acidifying " effect of anerobe, and the digestion of follow-up aerobic bacteria, is that nutriment is resolved into CO by the aerobic bacteria absorption with the organism after the anaerobism
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.In one-level settler 520, add caustic soda, 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 handled rises to about 4.5, therefore can regulate the pH value of coking chemical waste water according to the needs of subsequent processing steps.Different according to demand, one-level settler 520 can be various ways such as settling tower, settling tank, settler.
Anaerobic waste water biological treatment refers under condition of free-dioxygen by the anaerobion effect of (comprising double oxygen animalcule), and the various complicated organism decomposition and inversion in the waste water is become the process of materials such as methane and carbonic acid gas, 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 is hydrogen acceptor with chemical combination attitude oxygen, carbon, sulphur, nitrogen etc.
Anaerobic biological treatment is the chemistry of micro-organisms process of a complexity, relies on the bacterium of three big main monoids, i.e. the combined action of hydrolysis acid formers, hydrogen-producing acetogenic bacteria and methane-producing bacteria is finished.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 are hydrolyzed to earlier small molecules, dissolved organic matter under the effect of perienzyme, infiltrate in the cell paste then, be decomposed into small molecules, dissolved organic matter, infiltrate then in the cell paste, decompose generation VFA, alcohols, aldehydes etc.This stage mainly produces more senior lipid 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.
Biological denitrification is handled and is referred to that under anoxic environment, facultative anaerobe is with the NO in the 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
2O continues to be reduced to N then
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 oxygen deoxidation organic matter, 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
The multitube inner loop three phase fluidized bed reactor is a kind of novel fluidized-bed reactor, it is keeping the three-phase biologic fluidized-bed institute of tradition to have advantage: good mixing property in the reactor, rate of mass transfer is fast, sludge concentration is big, 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 microbial film thickness.In tradition was three-phase biologic fluidized-bed, gas speed and liquid speed all can not be very big, if surpass the terminal settling velocity of carrier widely, then because carrier is only done the motion of unidirectional upper reaches, and biomone will enter depositing separation area in a large number, therefore very easily took 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, because gas, liquid, solid are in the up-flow district and fall between the stream district and circulate, speed of circulation is very big, 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 microbial film thickness, increase with the inner transmission matter resistance of avoiding blocked up microbial film to cause, make circulating fluid bed middle microbial film keep higher activity.
2. the carrier current vector is few.Because circulating fluid bed turbulent fluctuation is sheared and friction can make blocked up microbial film come off voluntarily, 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, under situation about not refluxing, must adopt bigger aspect ratio, the diameter that is reactor must be little, highly bigger, and as long as circulating biological fluidized bed is up-flow tube 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 with fall between the 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 homogeneous, and this is very favourable for biomembranous good growth.
4. the transfer efficiency height of oxygen.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 the pipe, circulating liquid is carried under one's arms some small bubbles in the upspout to enter and is fallen the stream pipe, have only portion gas to overflow from the top, gas-liquid contact time is prolonged, so the oxygen-transfer efficiency height.
Inner loop three phase fluidized bed reactor also has the following advantages: relative catalytic oxidation COD holding capacity height, can not suppress biochemical because water inlet COD is too high; Resistance to flow is little, and air demand can reduce under the situation of same speed of circulation keeping, thereby has reduced 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 the 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 the 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 various ways such as settling tower, settling tank, settler.
Preferably, time of stopping in BAF 610 of coking chemical waste water is 12 hours.
BAF (BAF) is a kind of new bio embrane 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 big, 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(MBR), as the reuse water treatment process.Because the crown_interception of MBR has been avoided the loss of microorganism, can keep high sludge concentration in the bio-reactor, thereby improve volume load, has reduced sludge loading, has extremely strong impact resistance.Again because the crown_interception of film, SRT is prolonged, built and be conducive to breed microorganism growth slowly, as the environment of nitrobacteria growth, can improve the nitrated ability of system, be conducive to simultaneously improve the processing efficiency of difficult degradation larger molecular organics and impel it to decompose completely.In operational process, bigger waterpower circulation is conducive to the even mixing of sewage, thereby makes active sludge that good dispersiveness be arranged, and has improved processing efficiency and stability greatly.
Coking chemical waste water oxidation and biochemical processing device 500 comprehensive utilization catalytic oxidation and bio-oxidation technology, the effectively organism in the 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, setting device 120 is gone in the filtrate re-injection.
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 handling through coking chemical waste water oxidation and biochemical processing device 500 is filtered, the fine suspension in the 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 body formula, 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 the 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 big molecule of polarizability in the 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 body formula, 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 the bamboo charcoal, is preferably gac.Carbon leaching material has flourishing central hole structure and flourishing specific surface area, and loading capacity is big, 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 handling through secondary rough filtering device 720, keeps the turnover of total 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 the 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, enter secondary rough filtering device 720 again 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 filter core process external.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 the interior close outer structure of dredging of axle in five.One-level security personnel filtration unit 740 is provided with for the dispensing mouth of throwing in Scale inhibitors.
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 the interior close outer structure of dredging of axle in five.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 some composition sees through a kind of semi-permeable membranes-reverse osmosis membrane of selecting perviousness that has in the solution that desire separates under the effect of pressure, and collect in the low-tension side of film and see through thing, then 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 or is called infiltration from a kind of dilute solution to a kind of denseer flowing naturally of solution by a kind of semi-permeable membranes.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 then can make infiltration stop, the pressure when dilute solution stops to the infiltration of strong solution is called osmotic pressure.Reverse osmosis then 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 the 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 demonstration at random of specific conductivity is arranged, and have automatic warning 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 the clean water basin 800, can be back to greening or other process water; Dense water re-injection after the filtration is to setting device 120.
Dense water after one-level rough filtering device 710, secondary rough filtering device 720, nanofiltration device 750 and the 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 handling through coking wastewater deep treatment equipment 700 is lower, and the while can be removed the impurity in the 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 handled, can effectively remove suspended substance, organism and ammonia nitrogen in the 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 20mg/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 that one-level transition apparatus 730 and secondary transition apparatus 760 can omit, 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 may further comprise the steps:
Step S101, provide coking wastewater processing system 10.
Step S102, the bigger suspension oil of particle that uses oil removal device 110 to remove in the 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 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 flows into water knockout in the oil header then.The heavy oil that precipitates in the pond and other impurity accumulate in the pool bottom sludge bucket, enter in the sludge tank by shore pipe, and the waste water that the process oil removal is handled then overflow is gone into outside the discharge channel discharge pond, carries out subsequent disposal, to remove oil in water emulsion and other pollutents.
Preferably, coking chemical waste water stopped 2 h ~ 6 hours in oil removal device 110.
Need to prove, coking chemical waste water can use equalizing tank or surge tank (not shown) to handle before entering 110 processing of oil removal device, the waste water that enters oil removal device 110 is homogenized, it is stable that thereby assurance enters the water quality of the coking chemical waste water of oil removal device 110, therefore, equalizing tank or surge tank can be set before oil removal device 110.In the present embodiment, the volume ratio of equalizing tank or surge tank and oil removal device 110 is 1:5 ~ 1:3.
Preferably, use setting device to handle the coking chemical waste water of handling through oil removal device 110, the coking chemical waste water of handling through oil removal device 110 is homogenized.
Step S103, use air-floating apparatus 130 are removed suspended substance bigger in the 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 the waste water for carrier, and its small bubbles and object are looked as a whole, and its global density floats to the water surface on less than water, thereby realizes solid-liquid or liquid liquid separating process.Air-floating apparatus 130 can be preferably the flat flow air-floating apparatus for flat flow air-floating apparatus or flow lifting type air-floating apparatus.
Principle difference according to the microbubble generation, air-floating apparatus 130 can be aeration air-floating apparatus, dissolved air flotation device and electrofloatation device, as long as can remove the bigger suspended substance in the 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 the water and reaches capacity that 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 handling, also can be the recirculation water of air flotation pool water outlet, and the per-cent that the backflow water yield accounts for the water yield of handling claims reflux ratio, is the important factor that influences 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 oleaginousness is in 400mg/L in the coking chemical waste water, 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 h ~ 2 hours.
Preferably, the oleaginousness of the coking chemical waste water of process air-floating apparatus 130 processing is in 30mg/L.
Preferably, regulating the coking chemical waste water that homogenizes through setting device 120 used stripping tower 300 to remove in the coking chemical waste water with ammonium ion (NH before entering air-floating apparatus 130 earlier
4+) and free ammonia (NH
3) the nitrogen that exists of form.The coking chemical waste water that process stripping tower 300 is handled enters again to regulate in the setting device 120 and homogenizes, and then uses air-floating apparatus to remove bigger suspended substance in the coking chemical waste water.
Step S104, the emulsification shape coal tar that uses acid out device 140 further to remove in the coking chemical waste water.
The coking chemical waste water of discharging from air-floating apparatus 130 enters acid out device 140, and adding sulfuric acid is done acid out and handled the emulsification shape coal tar of further removing in the 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.
The content of coal tar can be avoided coal tar excessive in the coking chemical waste water that follow-up treatment facility is produced and destroy in 20mg/L after coking chemical waste water was handled through step S101 ~ step S104.
Step S105, use 510 pairs of coking chemical waste waters of one-level electrocatalysis oxidation apparatus to carry out catalytic oxidation, with improve in the 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 the acidic conditions, in 6～24V of catalytic oxidation low dc voltage electrostatic field, having under the condition of catalyzer existence, behind adjusting pH≤4, catalyzer was FeSO when catalytic oxidation was handled
4And H
2O
2
In this step, under acidic conditions, add FeSO
4And H
2O
2Generate the sub-OH of hydroxyl radical free radical simultaneously, 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 is by " hydrolysis " and " acidifying " effect of anerobe, and the digestion of follow-up aerobic bacteria, is that nutriment is resolved into CO by the aerobic bacteria absorption with the organism after the anaerobism
2And H
2O.
Step S106, the precipitation of using one-level settler 520 to remove in the coking chemical waste water.
Concrete, adopt the settling tower that has sludge bucket, finish precipitation process after leaving standstill to sedimentation of suspension to sludge bucket after the sewage that has a suspended substance enters.
Different according to demand, one-level settler 520 can be 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 the present embodiment, use sodium hydroxide solution to regulate pH value to 6.5 ~ 7.5 that are housed in the coking chemical waste water in the transition apparatus 530.Preferably, the mass concentration of sodium hydroxide solution is 7%.Need to prove that the pH value that is housed in transition apparatus 530 is not limited to be adjusted to 6.5 ~ 7.5, regulate the pH value that is housed in the coking chemical waste water in the transition apparatus 530 according to the requirement of subsequent disposal.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, yellow soda ash 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 be inorganics with the organism decomposition and inversion in the coking chemical waste water.Preferably, coking chemical waste water stopped 6 h ~ 12 hours in anaerobic device 540.
Anaerobic waste water biological treatment refers under condition of free-dioxygen by the anaerobion effect of (comprising double oxygen animalcule), and the various complicated organism decomposition and inversion in the waste water is become the process of materials such as methane and carbonic acid gas, 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 is hydrogen acceptor with chemical combination attitude oxygen, carbon, sulphur, nitrogen etc.
Anaerobic biological treatment is the chemistry of micro-organisms process of a complexity, relies on the bacterium of three big main monoids, i.e. the combined action of hydrolysis acid formers, hydrogen-producing acetogenic bacteria and methane-producing bacteria is finished.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 are hydrolyzed to earlier small molecules, dissolved organic matter under the effect of perienzyme, infiltrate in the cell paste then, be decomposed into small molecules, dissolved organic matter, infiltrate then in the cell paste, decompose generation VFA, alcohols, aldehydes etc.This stage mainly produces more senior lipid 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 handled.
Preferably, coking chemical waste water stopped 6 h ~ 12 hours in hypoxia device 550.
Biological denitrification is handled and is referred to that under anoxic environment, facultative anaerobe is with the NO in the 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
2O continues to be reduced to N then
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 oxygen deoxidation organic matter, 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 h ~ 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 handled.
Preferably, coking chemical waste water carries out before degree of depth catalytic oxidation handles, and 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 earlier.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 handles 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 the coking chemical waste water.
Different according to demand, two-stage precipitation device 580 can be various ways such as settling tower, settling tank, settler.
Preferably, in coking chemical waste water, add sodium hydroxide in this step.
Step S113,610 pairs of coking chemical waste waters of use BAF are handled.
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 handled.
Preferably, in the coking chemical waste water through step S101 ~ 114 processing, COD is down in the 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 the 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 in one-level is ensured public security filtration unit 740, to add Scale inhibitors in the process of one-level security personnel filtration.
Preferably, between step S116 and step S117, also comprise step: will inject first transition apparatus 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 in secondary is ensured public security filtration unit 770, to add Scale inhibitors in the process of secondary security personnel filtration.
Preferably, between step S118 and step S119, also comprise step: will inject 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 handle.
The coking chemical waste water of handling through osmosis filtration flows in the clean water basin 800, can be used for greening or other process water; Dense water re-injection after the filtration is to setting device 120.
Preferably, the dense water that obtains after step S115, step S116, step S118 and step S120 handle 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 setting device 120 is gone in the filtrate re-injection.
After the above-mentioned coking waste water treatment method of coking chemical waste water is handled, can effectively remove suspended substance, organism and ammonia nitrogen in the 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 utility model, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the utility model claim.Should be pointed out that for the person of ordinary skill of the art under the prerequisite that does not break away from the utility model design, can also make some distortion and improvement, these all belong to protection domain of the present utility model.Therefore, the protection domain of the utility model patent should be as the criterion with claims.
Claims (7)
1. a coking wastewater deep treatment equipment is used for coking chemical waste water is carried out advanced treatment, it is characterized in that, comprising:
One-level rough filtering device, described one-level rough filtering device are 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 handles;
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 deep treatment equipment according to claim 1 is characterized in that, the filtration apparatus that described one-level rough filtering device is the tank body formula.
3. coking wastewater deep treatment equipment according to claim 1 is characterized in that, the filtration apparatus that described secondary rough filtering device is the tank body formula.
4. coking wastewater deep treatment equipment according to claim 1 is characterized in that, also comprises the one-level transition apparatus, and described one-level transition apparatus is communicated with described one-level rough filtering device and secondary rough filtering device.
5. coking wastewater deep treatment equipment according to claim 4 is characterized in that, also comprises the secondary transition apparatus, and described secondary transition apparatus is communicated with described nanofiltration device and described secondary security personnel filtration unit.
6. coking wastewater deep treatment equipment according to claim 1 is characterized in that, described one-level security personnel filtration unit is provided with for the dispensing mouth of throwing in Scale inhibitors.
7. coking wastewater deep treatment equipment according to claim 1 is characterized in that, described secondary security personnel filtration unit is provided with for the dispensing mouth of throwing in Scale inhibitors.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108658291A (en) * | 2018-05-22 | 2018-10-16 | 重庆欣欣向荣精细化工有限公司 | A method of it reducing o-ethoxyphenol and produces Determination of Volatile Phenol in Refinery Wastewater content |
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2013
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108658291A (en) * | 2018-05-22 | 2018-10-16 | 重庆欣欣向荣精细化工有限公司 | A method of it reducing o-ethoxyphenol and produces Determination of Volatile Phenol in Refinery Wastewater content |
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