CN106277591A - Percolate nanofiltration concentrated solution processing method - Google Patents
Percolate nanofiltration concentrated solution processing method Download PDFInfo
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- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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Abstract
The present invention relates to a kind of percolate nanofiltration concentrated solution processing method, first warp is pressed nanofiltration to process and carry out minimizing, dope after centering pressure nanofiltration processes carries out coagulation air-float process, reclaim Humus larger molecular organics and carry out recycling, dope hardness after coagulation air-float processes is reduced by resin sofening treatment, dope after resin sofening treatment is processed through electrolytic oxidation, and backwash water is processed, clear liquid by middle pressure nanofiltration, water outlet after the water outlet of regeneration waste liquid alive and electrolytic oxidation is delivered to membrane biological reaction and is processed, the gas produced by electrolytic oxidation processes through tail gas absorption, qualified discharge after chlorine in tail gas is absorbed.Handling process of the present invention is reasonable, high treating effect, investment and operating cost are relatively low, avoid the problem that humic acid and hardness ions are accumulated in biochemical system, solve percolate nanofiltration concentrated solution and process a difficult problem, it is adaptable to process the nanofiltration concentrated solution that percolate " MBR+ nanofiltration " processing procedure produces.
Description
Technical field
The present invention relates to a kind of percolate nanofiltration concentrated solution processing method, belong to technical field of waste water processing.
Background technology
For landfill leachate treatment, " the consumer waste landfill percolate process engineering legislation " that Chinese Ministry of Environmental Protection issues
Recommend to use " pretreatment+biological treatment+advanced treating " group technology.Percolate, after biological treatment, needs to pass through again
NF membrane or reverse osmosis membrane advanced treating can qualified discharges.The concentration liquid measure that film unit produces is relatively big, accounts for percolate
About the 20% of volume, film-filter concentration liquid has the features such as organic concentration is high, salinity is high, biodegradability difference.
In landfill leachate treatment engineering, nanofiltration be mainly used in retaining bivalence or multivalent ion and molecular weight 300 with
On larger molecular organics, predominantly Humus material.The biochemical section that percolate processes at present uses biochemical and ultrafilter membrane group
The MBR technique closed, due to the main contamination characteristics of nanofiltration concentrated solution be COD, total nitrogen and hardness ions concentration high, direct process is to reaching
Difficulty is big, cost is high in mark discharge.
Currently for nanofiltration concentrated solution process main use method of recharging, membrane concentration method, evaporation-seasoning, coagulating sedimentation-
Advanced oxidation processes, electrochemical oxidation process etc..The method of recharging can cause building up of landfill yard Organic substance and salinity, but highly concentrated high salt
When percolate returns membrane bioreactor (MBR) degraded, membrane tube pressure can be caused to rise, system runs extremely unstable, causes place
Reason effect declines.Patent documentation CN1923875A, CN103964609 A and CN 103626314A all uses at membrane concentration method
Reason nanofiltration concentrated solution, but there is the problems such as operating pressure is high, energy consumption is high, producing water ratio is low, fouling membrane is serious, and membrane filtration in membrane concentration method
Concentrated solution still needs to process, and increases processing cost.Patent documentation CN103570157A and CN104211245A is to use evaporation
Processing nanofiltration concentrated solution, but the method investment is high, energy consumption is high, and evaporated residue is danger wastes, cost of disposal is high.Patent
Document CN101701025A and CN104478157 A all uses coagulating sedimentation-advanced oxidation processes to process nanofiltration concentrated solution, the method
It is directed to humic acid material removal effect good, but the organic nitrogen material of residual in concentrated solution, nitrate nitrogen can be oxidized into, go out
Water total nitrogen is difficult to up to standard.Patent documentation CN102701515A uses electrochemical oxidation process to process nanofiltration concentrated solution, and the method is not gone
Except the hardness ions in nanofiltration concentrated solution, permanent operation can cause electrolytic pole board, pipeline and reaction fouling blocking.
Summary of the invention
It is an object of the invention to provide a kind of high treating effect, can return to former biochemical system and be disposed, invest and run
Lower-cost percolate nanofiltration concentrated solution processing method.
The present invention is that the technical scheme reaching above-mentioned purpose is: a kind of percolate nanofiltration concentrated solution processing method, its
It is characterised by: carry out according to the following steps,
(1), middle pressure nanofiltration processes: the pH value of pending nanofiltration concentrated solution is controlled 6～6.5, by nanofiltration concentrated solution through height
Press pump is pressed in NF membrane element in sending into, and described middle pressure NF membrane element is at least two-part inner circulation structure, and middle pressure is received
The operation pressure of filter membrane component 10～20bar, through in press in NF membrane element segments formula after the membrane tube filtration treatment of circulation, general
The dope of 10～20wt% is circulated through circulating pump, remaining dope is delivered in coagulation floatation, and the clear liquid after process returns film
Bioreactor；
(2), coagulation air-float processes: add coagulation floatation after coagulant and flocculant being sufficiently mixed, or by coagulant and
Flocculant adds coagulation floatation and is sufficiently stirred for, and by air-dissolving air-float or scattered gas air supporting, makes dope produce scattered bubble
Stick on slaine and form humus flco swim in cell body liquid level, strike off the humus flco on cell body liquid level and reclaim
Utilizing, wherein said coagulant is slaine, and dosage is 100～1000mg/L, and described flocculant is organic polymer
Flocculant or microbial flocculant, dosage is 1～2mg/L；
(3), resin sofening treatment: the dope after being processed by coagulation air-float is sent in resin softening plant, is softened by resin
Dope is softened by the storng-acid cation exchange resin of device cationic exchange area, is being handed over by the calcium ions and magnesium ions in dope
Exchangeable ion generation ion-exchange reactions in changing district and in resin activity group, and the total hardness clearance ＞ in dope
60%；
(4), backwash water processes: after the storng-acid cation exchange resin of resin softening plant is saturated, with 3wt%～
The dilute hydrochloric acid of 5wt% carries out backwash and regeneration to strongly acidic cation exchange tree, and the regeneration liquid waste that backwash produces enters at backwash water
In reason device, processing with alkaline chemical precipitation, the mud after precipitation is carried out processed, it is biological that the water outlet after alkaline chemical precipitation returns film
Reactor；
(5), electrolytic oxidation processes: the dope after softened is squeezed in cell reaction groove by intake pump, in cell reaction groove
Electrolytic pole board anode-catalyzed oxidation degraded residue organic pollution be small organic molecule, simultaneously in electrolytic process in dope
Chloride ion to small organic molecule oxidative degradation and form carbon dioxide and water, water outlet after electrolysis returns membrane biological reaction
BOD/COD ＞ 0.3 in device, and water outlet carries out down pole after cell reaction groove runs 8～12h；
(6), tail gas absorption processes: hydrogen, chlorine and carbon dioxide are taken out in cell reaction groove by device for absorbing tail gas
Go out, and keep micro-vacuum state in cell reaction groove, up to standard after the chlorine in tail gas being absorbed with sodium hydrate aqueous solution
Discharge.
The present invention is directed to percolate its COD of nanofiltration concentrated solution, total nitrogen and the feature of hardness ions excessive concentration, first lead to
Press NF membrane unit to process in crossing, and middle pressure NF membrane element uses stagewise inner circulation structure, can make dope cross-flow
Filter, to increase the dope flow velocity on film surface, wash away and avoid pollutant in the accumulation on film surface, add among press NF membrane element
Operation Stress control 10～20bar, make middle pressure NF membrane element can run relatively stablely, reduce fouling membrane degree, warp
Receive concentrated liquor energy decrement to 40～60% after middle pressure nanofiltration membrane treatment, realize decrement owing to first passing through middle pressure NF membrane element
Change processes, therefore can reduce subsequent technique and process the water yield, reduces processing cost.After the present invention uses mixed condensed gas flotation process centering pressure nanofiltration
Dope be disposed, make dope produce scattered bubble adhesion on slaine and shape by air-dissolving air-float or scattered gas air supporting
Become humus flco to swim in cell body liquid level, can not only conveniently strike off the humus flco on cell body liquid level, can remove in dope
45～the Organic substance of 60%, solve current coagulant sedimentation and process in film-filter concentration liquid, because of coagulant and macromole humus shape
The flco precipitability become is poor, and controls the most at that time at coagulation stirring intensity, makes metallic salt flco meeting entrained air bubbles, in precipitation
Float in pond, cause water outlet SS higher and the problem for the treatment of effect decline.The present invention uses resin sofening treatment to coagulation air-float
Dope after process processes, and can solve follow-up dope problem of the easy fouling of electrolytic pole board when electrolytic oxidation processes, make
Water outlet after process does not results in hardness ions accumulation in returning membrane bioreactor, make membrane bioreactor stable, and
Keep the efficiency of biological treatment system.The present invention uses electrolytic oxidation to process dope, by cell reaction groove Inner electrolysis pole plate
Anode-catalyzed oxidation degraded residue organic pollution be small organic molecule, simultaneously in electrolytic process the chloride ion in dope to little
Molecular organic oxidative degradation also forms carbon dioxide and water, owing to carrying out at normal temperatures and pressures, and available nanofiltration concentrated solution
Chloride ion in former water reacts, it is not necessary to adds oxidant and flocculant, does not produce secondary pollution, high treating effect.And
After at electrolytic oxidation, the BOD/COD ＞ 0.3 in water outlet and water outlet, strengthen biodegradability.Method pair processed by the invention
Nanofiltration concentrated solution process after outlet water organic substance concentration and total hardness concentration be below the outlet water organic substance in membrane filtration clear liquid and
Total hardness concentration, effectively avoids the accumulation in membrane bioreactor of humus and hardness ions, and small organic molecule can
Removed by Aeration tank in membrane bioreactor, be converted into nitrate nitrogen owing to nitrogen pollutant is oxidized, can return to membrane biological reaction
Denitrification disposal is carried out in device.Originally enter invention and nanofiltration concentrated solution can be disposed into the acceptable degree of membrane bioreactor, and will
Former percolation liquid treatment membrane is sent in water outlet after the water outlet of clear liquid, backwash water and the alkaline chemical precipitation of middle pressure nanofiltration and electrolytic oxidation back to
Can dilute the former water of percolate, group technology high treating effect in bioreactor, investment and operating cost are relatively low.
Accompanying drawing explanation
Below in conjunction with the accompanying drawings embodiments of the invention are further described.
Fig. 1 is the flow chart of percolate nanofiltration concentrated solution processing method of the present invention.
Fig. 2 is the structural representation of percolate nanofiltration concentrated solution processing system of the present invention.
Fig. 3 is the structural representation of cell reaction groove of the present invention.
Fig. 4 is the profile of Fig. 3.
Wherein: 1 storage tank, 2 drain pipes, 3 high-pressure pumps, 4 circulating pumps, press NF membrane element in 5,6 control
Valve, 7 coagulation floatations, 8 water inlet pipes, 9 resin softening plants, 10 backwash water inlet pipes, 11 outlet pipes, 12 electrolysis
Reactive tank, 12-1 electrolysis bath, 12-2 electrolysis cycle pump, 12-3 dividing plate, 12-4 positive plate, 12-5 minus plate,
13 membrane bioreactors, 14 device for absorbing tail gas, 15 tracheas, 16 intake pumps, 17 regeneration liquid waste pipes, 18 backwashes
Water treatment facilities, 19 pipelines, 20 dope pipes, 21 circulation pipes.
Detailed description of the invention
Such as Fig. 1, shown in 2, the percolate nanofiltration concentrated solution processing method of the present invention, sequentially include the following steps:
(1), middle pressure nanofiltration processes.
Use nanofiltration concentrated solution produced by MBR+NF method process percolate to deposit and can carry out water quality and quantity to storage tank 1
Regulation, adds hydrochloric acid in storage tank 1 or sulphuric acid is sufficiently stirred for, and regulates the pH value of pending nanofiltration concentrated solution to 6～6.5,
So that postorder processes.As shown in Figure 2, storage tank 1 has inlet and liquid outlet, is provided with agitator, going out of storage tank 1 in storage tank 1
Liquid mouth is connected through the inlet of drain pipe 2 with middle pressure NF membrane element 5 and communicates, and is provided with high-pressure pump 3, nanofiltration on drain pipe 2
In concentrated solution presses NF membrane element 5 in high-pressure pump 3 is sent into.Pressing NF membrane element 5 in the present invention is at least interior circulation of two-part
Structure, and the operation pressure of middle pressure NF membrane element 5 is 10～20bar, the operation pressure such as middle pressure NF membrane element 5 exists
12bar or 15bar, middle pressure NF membrane element 5 can use existing rolling NF membrane, middle pressure NF membrane element 5 to be in dense water two
Three stage structure in segmentation structure or dense water, the membrane tube circulated in pressing NF membrane element segments formula in warp carries out filtration treatment, presses
Mass percent, 10～20wt% dopes are circulated through circulating pump 4, remaining dope is delivered in coagulation floatation 7, after process
Clear liquid returns membrane bioreactor 13.As shown in Figure 2, the dope outlet of NF membrane element of the present invention is connected to dope pipe 20, dope
Pipe 20 is connected with circulation pipe 21 and pipeline 19 by three way cock, equipped with the other end of circulation pipe 21 and the high-pressure pump 3 of circulating pump 4
Drain pipe 2 connection after outlet communicates the backflow that can carry out dense water, is provided with pipeline 19 and the coagulation air-float device 7 of control valve 6
Inlet connection communicates, and the clear liquid mouth of NF membrane element 5 connects the inlet of membrane bioreactor 13 by clear liquid pipe, therefore can
Control liquid circulation amount by control valve 6 is convenient, make dope at membrane tube surface cross flow filter, the dope stream on film surface can be increased
Speed, washes away and avoids pollutant in the accumulation on film surface.When the present invention uses 8 cun of nanofiltration membrane tube, concentrate circulating amount be up to 15～
20m3/ h, the dope after middle pressure nanofiltration being processed is delivered in coagulation floatation 7, through in receive concentrated liquor after pressure nanofiltration membrane treatment
Energy decrement is to 40～60%, and clear liquid returns membrane bioreactor 13 and is used for diluting the former water of percolate.Due to middle pressure nanofiltration clear liquid water
Matter is poor, and contained Organic substance contaminant molecule amount is less than 300, and its COD concentration is 300～600mg/L, far below the former water of percolate
COD value, returns middle pressure nanofiltration clear liquid to MBR system, can dilute the former water of percolate.
The present invention when middle pressure nanofiltration processes, the sustainable film antisludging agent that adds, film scale inhibitor dosing amount is 0.5～1L/h,
The present invention is when middle pressure nanofiltration processes, and central pressure NF membrane element 5 runs 12～24h clear water wash cycles once, during cleaning
Between be 5～10 minutes, to be maintained in middle pressure nanofiltration membrane treatment process, can prevent contaminate thing at film surface scale.And receive in middle pressure
Filter membrane component 5 runs every 6～within 12 months, uses chemical agent cleaning to be carried out, and presses in its membrane tube of NF membrane element 5 in elimination
Pollution, in holding press NF membrane element 5 permeant flux.
(2), coagulation air-float processes.
Add coagulation floatation 7 after coagulant and flocculant being sufficiently mixed, or coagulant and flocculant are added coagulation
Flotation tank 7 is sufficiently stirred for, and by air-dissolving air-float or scattered gas air supporting, makes dope produce scattered bubble adhesion on slaine
And form humus flco and swim in cell body liquid level, coagulant of the present invention is slaine, and this slaine can use iron salt or aluminum
Salt, as used ferric chloride, ferrous sulfate hydrate and bodied ferric sulfate etc., its dosage is 100～1000mg/L, and wads a quilt with cotton
Solidifying agent is organic polymer coargulator or microbial flocculant, and dosage is 1～2mg/L.The present invention can use existing molten
Air flotation device or scattered air flotation device make the dope in coagulation floatation 7 produce the bubble adhesion of high degree of dispersion at slaine
On, strike off the humus flco on cell body liquid level by Slag Scraping Device and recycle, a large amount of humus in dope are removed, and dense
Liquid is added in resin softening plant 9 by water inlet pipe 8, and the present invention is after coagulation air-float processes, to Organic substance in dope (COD)
Clearance up to 45～60%, the humus sludge after striking off is collected, it is achieved recycling.
(3), resin sofening treatment.
By coagulation air-float process after dope send into resin softening plant 9, as shown in Figure 2, coagulation air-float process after dense
Liquid adds the top to resin softening plant 9, by the strong acid of resin softening plant 9 cationic exchange area by water inlet pipe 8
Dope is softened by property cation exchange resin, by the calcium ions and magnesium ions in dope in cation exchange area with resin activity base
Exchangeable ion generation ion-exchange reactions in group, with the hydrion in resin, sodium ion for exchange product, softens through resin
After, make the total hardness clearance ＞ 60% in dope, bottom resin softening plant 9, be provided with outlet, going out of resin softening plant 9
The mouth of a river is added in cell reaction groove 12 by outlet pipe 11 and intake pump 16.The present invention uses resin sofening treatment to coagulation air-float
Dope after process processes, and can guarantee that follow-up electrolytic oxidation section non flouling behaviour, water outlet after treatment return membrane bioreaction
Answer and device 13 does not results in hardness ions accumulation, solve current membrane tube pressure and rise, the problem of system fluctuation of service.
(4), backwash water processes.
After the storng-acid cation exchange resin of resin softening plant 9 is saturated, the dilute hydrochloric acid with 3～5wt% is to strong acid
Property cation exchange tree carry out backwash and regeneration, as shown in Figure 2, this dilute hydrochloric acid by backwash water inlet pipe 10 from resin softening plant 9
Bottom enter, strongly acidic cation exchange tree is carried out backwash and regeneration, the regeneration liquid waste that backwash produces is from resin softening plant 9
Top is discharged, and the regeneration liquid waste that backwash produces enters in backwash water processing means 18 by regeneration liquid waste pipe 17, and backwash water processes
It is provided with agitator in device 18, bottom backwash water processing means 18, is provided with sludge outlet, the outlet of backwash water processing means 18
Connect the inlet of membrane bioreactor 13 by water pipe, use alkaline chemical precipitation method that regeneration liquid waste is processed, can be by regenerated
Liquid pH value controls 10～11, and the mud after precipitation is carried out processed, or the biochemistry by mud Yu percolation liquid treating system
Excess sludge mixing carries out processed, and the water outlet after alkaline chemical precipitation returns membrane bioreactor 13.The present invention can use Calx
Regeneration liquid waste is processed by method, lime-soda process or lime stone-gypsum method, after being disposed by alkaline chemical precipitation method, and effluent quality
In order, pollutant load is the lowest.
(5), electrolytic oxidation processes.
Dope after softened squeezes into the electrolytic pole board in cell reaction groove 12, in cell reaction groove 12 by intake pump 16
Anode-catalyzed oxidation degraded residue organic pollution be small organic molecule, the chloride ion pair in dope in electrolytic process simultaneously
Small organic molecule oxidative degradation also forms carbon dioxide and water, and the water outlet after electrolysis returns membrane bioreactor 13, in electrolysis
Reactive tank 12 carries out down pole after running 8～12h.Due to the dope after coagulation air-float and resin soften, to contain molecular weight relatively low
Hardly degraded organic substance, the direct catalyzing and degrading pollutant of anode, electrolysis produces the indirect degradation of contaminant of strong oxidizer, i.e. utilizes dense
The oxidisability of chloride ion electrolysate chlorine in liquid, is carbon dioxide and water and water outlet by hardly degraded organic substance direct oxidation
In BOD/COD ＞ 0.3, the biodegradability of waste water can be improved.
Its course of reaction of electrolytic anode Direct Catalytic Oxidation of the present invention is as follows: reductive organic matter → small organic molecule+e~。
When the catalysis oxidation leading with chloride, its course of reaction is as follows:
2Cl-→Cl2+2e-；
Cl2+H2O→HClO+Cl-+H+；
HClO→H++ClO-；
ClO-+ larger molecular organics → CO2+H2O+Cl-；
ClO-+ larger molecular organics → small organic molecule+Cl-；
ClO-+ organic nitrogen → NO3-+Cl-。
As shown in Fig. 2～4, cell reaction groove 12 of the present invention is integrally closed structure, cell reaction groove 12 have multiple solely
Vertical and the electrolysis bath 12-1 communicated that is in series along liquid flow direction, anterior electrolysis bath 12-1 and last electrolysis bath 12-1 lead to
Cross electrolysis cycle pump 12-2 connection to communicate, there is in each electrolysis bath 12-1 the electrolytic pole board of multiple series connection, cell reaction groove 12
Liquid outlet is connected with the inlet of membrane bioreactor 13 is communicated by water pipe, after the process of cell reaction groove 12 electrolytic oxidation
Water outlet returns membrane bioreactor 13 and is used for diluting the former water of percolate, and cell reaction groove 12 top is inhaled with tail gas by trachea 15
The air inlet of receiving apparatus 14 connects.Owing to cell reaction groove 12 is integrally closed, only retain passage, generation will be aoxidized during electrolysis
Hydrogen, chlorine and carbon dioxide by device for absorbing tail gas 14 sucking-off.
As shown in Fig. 2～4, cell reaction groove 12 of the present invention is provided with at least two row electrolysis bath 12-1, and the electrolysis bath of front portion
12-1 and last electrolysis bath 12-1 is positioned at same one end being connected by electrolysis cycle pump 12-2 and communicates, and takes up an area space to reduce,
It is provided with the dividing plate 12-3 of upper and lower misaligned interval in each electrolysis bath 12-1 along liquid flow direction, in each electrolysis bath 12-1, forms liquid
The crossing type runner up and down that body passes through, and increase the dope flow channel length by electrolysis bath 12-1, can fully carry out electrolytic oxidation
Process.Electrolytic pole board in the present invention each electrolysis bath 12-1 includes 20～50 positive plate 12-4 and 20～50 corresponding negative electrodes
Plate 12-5, and positive plate 12-4 has titanio ruthenium oxide oxidation iridium coating layer, minus plate 12-5 uses corrosion resistant plate, as used
316L corrosion resistant plate, the spacing between positive plate 12-4 and minus plate 12-5 is 1～2cm.Positive plate 12-4 of the present invention and negative electrode
The specification of plate 12-5 is 0.3m × 0.8m, and thickness is 1.5mm, by the DC voltage-stabilizing pulse power as power supply, work
Time decomposition voltage be 10～30V, Faradaic current is 50～200A, and circular flow is 20～50 times of flow of inlet water, with ensure
Electrolytically generated oxide is sufficiently mixed utilization.It is at room temperature that cell reaction groove 12 of the present invention dope carries out electrolytic oxidation processes
Carry out under normal pressure, and utilize the chloride ion in the former water of nanofiltration concentrated solution to react, it is not necessary to add oxidant and flocculant, no
Secondary pollution can be produced.The present invention carries out down pole after electrolysis runs 8～12h, and the water outlet after electrolysis returns film by return pipe
Bioreactor 13.
Nanofiltration concentrated solution is disposed to the acceptable degree of membrane bioreactor 13 by the present invention, the clear liquid of central pressure nanofiltration,
Water outlet film feeding bioreactor 13 after the water outlet of backwash water process and electrolytic oxidation process is received with percolate and is carried out MBR
+ NF method processes, and after electrolytic oxidation, owing to the BOD/COD ratio of water outlet is promoted to more than 0.3 by 0.03, biodegradability strengthens,
Small organic molecule in water outlet can be removed by Aeration tank in membrane bioreactor 13, and the nitrate nitrogen in electrolysis water outlet then passes through
In membrane bioreactor 13, denitrification pond is converted into nitrogen and removes, it is to avoid tired in biochemical system of humus and hardness ions
Long-pending, high treating effect, investment and operating cost are relatively low.
(6), tail gas absorption processes: by device for absorbing tail gas 14 by hydrogen, chlorine and carbon dioxide from cell reaction groove 12
Interior extraction, and keep micro-vacuum state in cell reaction groove 12, this device for absorbing tail gas 14 can use protected against explosion water to spray vacuum
Unit, qualified discharge after the chlorine in tail gas being absorbed with sodium hydrate aqueous solution, device for absorbing tail gas 14 of the present invention
Note sodium hydrate aqueous solution in water tank, sodium hydrate aqueous solution is the sodium hydrate aqueous solution of 10～40wt% concentration.Can determine
The concentration of phase detection sodium hydrate aqueous solution, to ensure assimilation effect.
Embodiment 1
Certain percolate from garbage filling field treatment plant treating capacity is 500m3/ d, uses MBR+NF method to process percolate, produces
Raw 100m3/ d nanofiltration concentrated solution, detects nanofiltration concentrated solution, its COD at the ratio of 3000mg/L, BOD/COD 0.03, chlorine from
Son is at 6000mg/L, total hardness 7000mg/L, ammonia nitrogen 10mg/L, total nitrogen 300mg/L.
Processing by the percolate nanofiltration concentrated solution processing method of the present invention, nanofiltration concentrated solution send through high-pressure pump 3
Entering in pressure NF membrane element 5, carry out middle pressure nanofiltration and process, the operation pressure of middle pressure NF membrane element 5 is at 15bar, producing water ratio
Being 50%, circulating pump 4 flow is at 16m3/ h, middle pressure NF membrane element 5 is three stage structure in dense water, by nanofiltration concentrated solution pH value
Regulation, 6～6.5, uses 8 cun of rolling NF membrane, is circulated by 15wt% dope after process, and remaining delivers to coagulation floatation 7
In, nanofiltration aquifer yield is 50m3About/d, runs 18h by clear water wash cycles once, and scavenging period is 6 minutes, after process
Clear liquid returns membrane bioreactor 13 and is used for diluting the former water of percolate, and pressure nanofiltration clear liquid COD is 500mg/L, and matter situation is superior to
Ultrafiltration clear liquid.
Dope after centering pressure nanofiltration processes is detected by GB16889-2008, and its COD is at 5000mg/L, BOD/COD
Ratio 0.01, chloride ion is in 6000mg/L, total hardness 8000mg/L, and ammonia nitrogen is at 10mg/L, and total nitrogen is at 450mg/L.
Dope after middle pressure nanofiltration being processed is delivered to, in coagulation floatation 7, add after coagulant and flocculant being sufficiently mixed
Entering coagulation floatation 7, coagulant is iron salt, can use ferric chloride, ferrous sulfate hydrate or bodied ferric sulfate wherein it
One or its mixing, its dosage is 500mg/L, and flocculant is organic polymer coargulator or microbial flocculant, dosage
For 1.5mg/L, after air-dissolving air-float or scattered gas air supporting, strike off the humus flco on cell body liquid level with Slag Scraping Device, and will scrape
Humus sludge after removing is collected, it is achieved recycling.Water outlet after processing coagulation air-float detects, its COD
At the ratio of 2500mg/L, BOD/COD 0.03, chloride ion at 6200mg/L, total hardness 8000mg/L, ammonia nitrogen 10mg/L, always
Nitrogen 350mg/L.
Water outlet after being processed by coagulation air-float is sent in resin softening plant 9, by the highly acid in resin softening plant 9
Dope is softened by cation exchange resin, detects dope after softening, and its COD is at the ratio of 2500mg/L, BOD/COD
Value is 0.03, and chloride ion is in 6200mg/L, total hardness 2000mg/L, and ammonia nitrogen is at 5mg/L, and total nitrogen is at 300mg/L.
After the storng-acid cation exchange resin of resin softening plant 9 is saturated, with the dilute hydrochloric acid of 3wt% to highly acid sun
Amberlite carries out backwash and regeneration, carries out alkaline chemical precipitation process, is controlled by regeneration liquid waste pH value 10～11, after precipitation
Mud carries out processed, or is mixed with the biochemical excess sludge of percolation liquid treating system by mud and carry out processed, water outlet
Returning in membrane bioreactor 13, its COD of water outlet after backwash water processes is 100mg/L, and water quality condition is superior to ultrafiltration clear liquid.
Dope after softened is squeezed in cell reaction groove 12 by intake pump 16, and electrolysis cycle pump 12-2 flow is
60m3/ h, has 30 positive plate 12-4 and 30 corresponding minus plate 12-5, positive plate 12-4 and the moon in each electrolysis bath 12-1
The specification of pole plate 12-5 is 0.3m × 0.8m, and thickness is 1.5mm, and the spacing between positive plate 12-4 and minus plate 12-5 is
1.5cm, during work, decomposition voltage is 20V, and Faradaic current is 100A, and electrolysis carries out down pole once, to electrolytic oxidation after running 10h
Water outlet after process detects, and its COD is at the ratio of 500mg/L, BOD/COD at ＞ 0.03, and chloride ion is at 6000mg/L, always
Hardness 1500mg/L, ammonia nitrogen is at 5mg/L, and total nitrogen is at 300mg/L, and the water outlet after electrolytic oxidation processes returns membrane bioreactor
13。
Hydrogen, chlorine and the carbon dioxide produced when electrolytic oxidation processes passes through device for absorbing tail gas 14 from cell reaction groove
The top of 12 is extracted out, qualified discharge after absorbing the chlorine in tail gas with the sodium hydrate aqueous solution of 20wt% concentration.
Water outlet film feeding after the clear liquid of middle pressure nanofiltration, backwash water alkaline chemical precipitation water outlet water and electrolytic oxidation being processed is biological
Reactor 13 and percolate are received and are carried out MBR+NF process, after electrolytic oxidation, owing to the BOD/COD ratio of water outlet is by 0.03
Being promoted to more than 0.3, biodegradability strengthens, and the small organic molecule in water outlet can be gone by Aeration tank in membrane bioreactor 13
Removing, the nitrate nitrogen in electrolysis water outlet is then converted into nitrogen by denitrification pond in membrane bioreactor 13 and removes.Obtain after processing
To clear liquid detect, its COD can meet GB16889-at 5mg/L, total nitrogen in 30mg/L, water outlet at 80mg/L, ammonia nitrogen
2008 table 2 discharge standards.
Embodiment 2
Processing by the percolate nanofiltration concentrated solution processing method of the present invention, nanofiltration concentrated solution send through high-pressure pump 3
Entering in pressure NF membrane element 5, carry out middle pressure nanofiltration and process, the operation pressure of middle pressure NF membrane element 5 is at 20bar, producing water ratio
Being 55%, circulating pump 4 flow is at 20m3/ h, two-period form structure in the dense water of middle pressure NF membrane element 5, nanofiltration concentrated solution pH value is adjusted
Joint, 6～6.5, uses 8 cun of rolling NF membrane, is circulated by 18wt% dope after process, and remaining delivers to coagulation floatation 7
In, persistently adding film antisludging agent, film scale inhibitor dosing amount is 0.8L/h, and middle pressure nanofiltration aquifer yield is 50m3About/d, runs 20h
By clear water wash cycles once, scavenging period is 8 minutes, and the clear liquid after process returns membrane bioreactor 13 and is used for diluting diafiltration
The former water of liquid, middle pressure nanofiltration clear liquid COD is 300mg/L, and matter situation is superior to ultrafiltration clear liquid.
Concentrated solution after centering pressure nanofiltration processes is detected by GB16889-2008, and its COD is at 5500mg/L, BOD/
The ratio of COD is 0.01, and chloride ion is in 6000mg/L, total hardness 8000mg/L, and ammonia nitrogen is at 10mg/L, and total nitrogen is at 450mg/L.
Dope after middle pressure nanofiltration being processed is delivered to, in coagulation floatation 7, add after coagulant and flocculant being sufficiently mixed
Entering coagulation floatation 7, coagulant is iron salt, can use ferric chloride, ferrous sulfate hydrate or bodied ferric sulfate wherein it
One or its mixing, its dosage is 800mg/L, and flocculant is organic polymer coargulator or microbial flocculant, dosage
For 1.5mg/L；After air-dissolving air-float or scattered gas air supporting, strike off the humus flco on cell body liquid level with Slag Scraping Device, and will scrape
Humus sludge after removing is collected, it is achieved recycling.And the water outlet after processing coagulation air-float detects, its
COD at the ratio of 2200mg/L, BOD/COD 0.03, chloride ion at 6200mg/L, total hardness 8000mg/L, ammonia nitrogen 10mg/L,
Total nitrogen 350mg/L.
Dope after being processed by coagulation air-float sends into resin softening plant 9, by the highly acid sun in resin softening plant 9
Dope is softened by ion exchange resin, detects dope after softening, and its COD is at the ratio of 2200mg/L, BOD/COD
0.03, chloride ion is in 6200mg/L, total hardness 1000mg/L, and ammonia nitrogen is at 5mg/L, and total nitrogen is at 300mg/L.
After the storng-acid cation exchange resin of resin softening plant 9 is saturated, with the dilute hydrochloric acid of 5wt% to highly acid sun
Amberlite carries out backwash and regeneration, controls regeneration liquid waste pH value, 10～11, to be dehydrated the mud after alkaline chemical precipitation
Process, or mud is mixed with the biochemical excess sludge of percolation liquid treating system carry out processed, water outlet return membrane bioreaction
In answering device 13, its COD of water outlet after backwash water processes is 100mg/L, and water quality condition is superior to ultrafiltration clear liquid.
Dope after softened is squeezed in cell reaction groove 12 by intake pump 16, and electrolysis cycle pump 12-2 flow is
80m3/ h, has 40 positive plate 12-4 and 40 corresponding minus plate 12-5, positive plate 12-4 and the moon in each electrolysis bath 12-1
The specification of pole plate 12-5 is 0.3m × 0.8m, and thickness is 1.5mm, and the spacing between positive plate 12-4 and minus plate 12-5 is
1.5cm, during work, decomposition voltage is 20V, and Faradaic current is 100A, and electrolysis carries out down pole once, to electrolytic oxidation after running 10h
Water outlet after process detects, and COD is at the ratio of 400mg/L, BOD/COD at ＞ 0.03, and chloride ion is at 6000mg/L, the most firmly
Degree 800mg/L, ammonia nitrogen is at 5mg/L, and total nitrogen is at 300mg/L, and return membrane bioreactor 13 is led in the water outlet after electrolytic oxidation processes.
Electrolytic oxidation processes hydrogen, chlorine and the carbon dioxide produced by device for absorbing tail gas 14 from cell reaction groove 12
Top extract out, qualified discharge after the chlorine in tail gas being absorbed with the sodium hydrate aqueous solution of 30wt% concentration.
Water outlet film feeding biological respinse after the water outlet that the clear liquid of middle pressure nanofiltration, backwash water are processed and electrolytic oxidation process
Device 13 and percolate are received and are carried out MBR+NF method process, after electrolytic oxidation, owing to the BOD/COD ratio of water outlet is carried by 0.03
Rising to more than 0.3, biodegradability strengthens, and the small organic molecule in water outlet can be gone by Aeration tank in membrane bioreactor 13
Removing, the nitrate nitrogen in electrolysis water outlet is then converted into nitrogen by denitrification pond in membrane bioreactor 13 and removes.After processing
Clear liquid detects, and its COD can meet GB16889-2008 table 2 at 5mg/L, total nitrogen in 30mg/L, water outlet at 80mg/L, ammonia nitrogen
Discharge standard, can make former percolation liquid treatment membrane bio-reaction system energy stable operation.
Claims (10)
1. a percolate nanofiltration concentrated solution processing method, it is characterised in that: carry out according to the following steps,
(1), middle pressure nanofiltration processes: the pH value of pending nanofiltration concentrated solution is controlled 6～6.5, by nanofiltration concentrated solution through high-pressure pump
Pressing in NF membrane element in feeding, described middle pressure NF membrane element is at least two-part inner circulation structure, and middle pressure NF membrane
The operation pressure of element 10～20bar, through in press the membrane tube filtration treatment circulated in NF membrane element segments formula after, by 10～
The dope of 20wt% is circulated through circulating pump, remaining dope is delivered in coagulation floatation, and it is biological that the clear liquid after process returns film
Reactor；
(2), coagulation air-float processes: add coagulation floatation after coagulant and flocculant being sufficiently mixed, or by coagulant and flocculation
Agent adds coagulation floatation and is sufficiently stirred for, and by air-dissolving air-float or scattered gas air supporting, makes dope produce scattered bubble adhesion
On slaine and form humus flco and swim in cell body liquid level, strike off the humus flco on cell body liquid level and reclaim profit
With, wherein said coagulant is slaine, and dosage is 100～1000mg/L, and described flocculant is organic polymer wadding
Solidifying agent or microbial flocculant, dosage is 1～2mg/L；
(3), resin sofening treatment: the dope after being processed by coagulation air-float is sent in resin softening plant, by resin softening plant
Dope is softened by the storng-acid cation exchange resin of cationic exchange area, by the calcium ions and magnesium ions in dope in exchange area
In with the exchangeable ion generation ion-exchange reactions in resin activity group, and the total hardness clearance ＞ 60% in dope；
(4), backwash water processes: after the storng-acid cation exchange resin of resin softening plant is saturated, with 3wt%'s～5wt%
Dilute hydrochloric acid carries out backwash and regeneration to strongly acidic cation exchange tree, and the regeneration liquid waste that backwash produces enters backwash water processing means
In, processing by alkaline chemical precipitation method, the mud after precipitation is carried out processed, the water outlet after alkaline chemical precipitation returns membrane biological reaction
Device；
(5), electrolytic oxidation processes: the dope after softened squeezes into the electricity in cell reaction groove, in cell reaction groove by intake pump
The anode-catalyzed oxidation degraded residue organic pollution solving pole plate is small organic molecule, the chlorine in dope in electrolytic process simultaneously
Ion pair small organic molecule oxidative degradation also forms carbon dioxide and water, and the water outlet after electrolysis returns membrane bioreactor, and
BOD/COD ＞ 0.3 in water outlet, carries out down pole after cell reaction groove runs 8～12h；
, tail gas absorption process: by device for absorbing tail gas, hydrogen, chlorine and carbon dioxide are extracted out in cell reaction groove,
And keep micro-vacuum state in cell reaction groove, row up to standard after the chlorine in tail gas being absorbed with sodium hydrate aqueous solution
Put.
Percolate nanofiltration concentrated solution processing method the most according to claim 1, it is characterised in that: described receive in middle pressure
When filter processes, persistently add film antisludging agent, and film scale inhibitor dosing amount is 0.5～1L/h.
Percolate nanofiltration concentrated solution processing method the most according to claim 1, it is characterised in that: described receive in middle pressure
When filter processes, central pressure NF membrane element runs in 12～24h clear water wash cycles and presses NF membrane element once, scavenging period
It it is 5～10 minutes.
Percolate nanofiltration concentrated solution processing method the most according to claim 1, it is characterised in that: described receive in middle pressure
When filter processes, central pressure NF membrane element runs every 6～within 12 months, uses chemical agent cleaning to be carried out, to eliminate in membrane tube
Pollution.
Percolate nanofiltration concentrated solution processing method the most according to claim 1, it is characterised in that: described at coagulation gas
After floating process, the COD clearance in dope is 45～60%.
Percolate nanofiltration concentrated solution processing method the most according to claim 1, it is characterised in that: described soft at resin
After change processes, dope total hardness clearance is more than 60%.
Percolate nanofiltration concentrated solution processing method the most according to claim 1, it is characterised in that: described in tail gas suction
Receipts process, and sodium hydrate aqueous solution is the sodium hydrate aqueous solution of 10～40wt% concentration.
Percolate nanofiltration concentrated solution processing method the most according to claim 1, it is characterised in that: described electrolysis is anti-
Answering groove is integrally closed structure, and cell reaction groove has the multiple independent and electrolysis bath communicated that is in series along liquid flow direction,
And the electrolysis bath of front portion and last electrolysis bath are connected by electrolysis cycle pump and communicate, there is in each electrolysis bath the electrolysis of multiple series connection
Pole plate, the liquid outlet of cell reaction groove is connected with the inlet of membrane bioreactor is communicated by water pipe, cell reaction groove top
It is connected with the air inlet of device for absorbing tail gas by trachea.
Percolate nanofiltration concentrated solution processing method the most according to claim 1, it is characterised in that: described each electrolysis bath
The interior dividing plate being provided with upper and lower misaligned interval along liquid flow direction, has the crossing type stream up and down that liquid passes through in each electrolysis bath
Road.
Percolate nanofiltration concentrated solution processing method the most according to claim 1, it is characterised in that: described each electrolysis
Electrolytic pole board in groove includes 20～50 positive plates and 20～50 corresponding minus plates, and positive plate has titanio oxidation
Ruthenium yttrium oxide coating, minus plate uses corrosion resistant plate, and the spacing between positive plate and minus plate is 1～2cm.
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Address after: 213025 No. 156 Hanjiang Road, Changzhou City, Jiangsu Province Patentee after: Welly Environmental Technology Group Co., Ltd. Address before: 213125 Hanjiang Road, Xinbei District, Jiangsu, Changzhou, China, No. 156 Patentee before: Jiangsu Welle Environmental Protection Technology Co., Ltd. |