CN106277591B - Landfill leachate nanofiltration concentrate processing method - Google Patents
Landfill leachate nanofiltration concentrate processing method Download PDFInfo
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- CN106277591B CN106277591B CN201610737468.8A CN201610737468A CN106277591B CN 106277591 B CN106277591 B CN 106277591B CN 201610737468 A CN201610737468 A CN 201610737468A CN 106277591 B CN106277591 B CN 106277591B
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F9/00—Multistage treatment of water, waste water or sewage
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- C02F2103/06—Contaminated groundwater or leachate
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- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
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Abstract
The present invention relates to a kind of landfill leachate nanofiltration concentrate processing methods, first pressure nanofiltration processing carries out minimizing in warp, centering presses nanofiltration treated dope to carry out coagulation air-float processing, it recycles Humus larger molecular organics and carries out resource utilization, dope hardness after coagulation air-float is handled is reduced by resin sofening treatment, by the dope after resin sofening treatment through electrolytic oxidation process, and backwash water is handled, by the clear liquid of middle pressure nanofiltration, the water outlet and the water outlet after electrolytic oxidation for regenerating waste liquid living are sent to membrane biological reaction processing, the gas that electrolytic oxidation generates is handled through tail gas absorption, qualified discharge after being absorbed to the chlorine in tail gas.Process flow of the present invention is reasonable, high treating effect, investment and operating cost are lower, avoid humic acid and the problem of hardness ions are accumulated in biochemical system, it solves landfill leachate nanofiltration concentrate processing problem, is suitable for handling the nanofiltration concentrate of landfill leachate " MBR+ nanofiltration " treatment process generation.
Description
Technical field
The present invention relates to a kind of landfill leachate nanofiltration concentrate processing methods, belong to technical field of waste water processing.
Background technique
For landfill leachate treatment, " the consumer waste landfill percolate processing engineering legislation " of Chinese Ministry of Environmental Protection's publication
Recommend to use " pretreatment+biological treatment+advanced treating " group technology.Landfill leachate after biological treatment, need using
Nanofiltration membrane or reverse osmosis membrane advanced treating can qualified discharges.The concentration liquid measure that film unit generates is larger, accounts for about landfill leachate
20% or so of volume, film-filter concentration liquid have the characteristics that organic concentration is high, salinity is high, biodegradability is poor.
In landfill leachate treatment engineering, nanofiltration be mainly used for retaining divalent or multivalent ion and molecular weight 300 with
On larger molecular organics, predominantly humus material.The biochemical section of percolate processing at present is using biochemical and ultrafiltration membrane group
The MBR technique of conjunction, since the main contamination characteristics of nanofiltration concentrate are that COD, total nitrogen and hardness ions concentration are high, directly processing is to reaching
Mark discharge difficulty is big, at high cost.
Currently, mainly using recharge method, membrane concentration method, evaporation-seasoning, coagulating sedimentation-for nanofiltration concentrate processing
Advanced oxidation processes, electrochemical oxidation process etc..Recharge method will cause building up for landfill yard organic matter and salinity, but highly concentrated with high salt
When percolate returns to membrane bioreactor (MBR) degradation, the rising of membrane tube pressure will cause, system operation is extremely unstable, causes to locate
Manage effect decline.Patent document CN1923875A, CN103964609 A and CN 103626314A are all made of membrane concentration method to locate
Manage nanofiltration concentrate, but membrane concentration method there are operating pressures it is high, energy consumption is high, producing water ratio is low, fouling membrane is serious the problems such as, and membrane filtration
Concentrate still needs to handle, and increases processing cost.Patent document CN103570157A and CN104211245A are using evaporation
Nanofiltration concentrate is handled, but this 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 are all made of coagulating sedimentation-advanced oxidation processes processing nanofiltration concentrate, this method
It is good to be directed to humic acid material removal effect, but remaining organic nitrogen material in concentrate, nitrate nitrogen can be oxidized into, out
Water total nitrogen is difficult to up to standard.Patent document CN102701515A handles nanofiltration concentrate using electrochemical oxidation process, and this method is not gone
Except the hardness ions in nanofiltration concentrate, permanent operation will cause electrolytic pole board, pipeline and reaction fouling blocking.
Summary of the invention
The object of the present invention is to provide a kind of high treating effects, can return to former biochemical system and are disposed, invest and run
Lower-cost landfill leachate nanofiltration concentrate processing method.
The technical solution of the present invention in order to achieve the above objectives is: a kind of landfill leachate nanofiltration concentrate processing method,
It is characterized in that: carrying out according to the following steps,
(1), middle pressure nanofiltration processing: the pH value of nanofiltration concentrate to be processed is controlled 6~6.5, by nanofiltration concentrate through height
Press pump is pressed in nanofiltration membrane component in being sent into, and the middle pressure nanofiltration membrane component be at least two-part inner circulation structure, and middle press is received
The operating pressure of filter membrane component is in 10~20bar, will after the membrane tube filtration treatment recycled in nanofiltration membrane element segments formula is pressed in
The dope of 10~20wt% is recycled through circulating pump, remaining dope is sent to coagulation floatation, and treated, and clear liquid returns to film
Bioreactor；
(2), coagulation air-float is handled: be added coagulation floatation after coagulant and flocculant are sufficiently mixed, or by coagulant and
Flocculant is added coagulation floatation and is sufficiently stirred, and by air-dissolving air-float or air-dispersing air bearing, dope is made to generate the bubble of dispersion
It is adhered on metal salt and forms humus wadding body and swim in pond body liquid level, strike off the humus wadding body on pond body liquid level and recycle
It utilizes, wherein the coagulant is metal salt, dosage is 100~1000mg/L, and the flocculant is organic polymer
Flocculant or microbial flocculant, dosage are 1~2mg/L；
(3), resin sofening treatment: coagulation air-float treated dope is sent into resin softening plant, is softened by resin
The storng-acid cation exchange resin of device middle-jiao yang, function of the spleen and stomach ion-exchange area softens dope, and the calcium ions and magnesium ions in dope are being handed over
It changes and ion-exchange reactions, and the total hardness removal rate > in dope occurs in area with the exchangeable ion in resin activity group
60%；
(4), backwash water process: resin softening plant storng-acid cation exchange resin saturation after, 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 generates enters at backwash water
It manages in device, is handled with alkaline chemical precipitation, the sludge after precipitating is carried out dehydrating, the water outlet after alkaline chemical precipitation returns to film biology
Reactor；
(5), electrolytic oxidation process: the dope after softened is squeezed into cell reaction slot by intake pump, in cell reaction slot
The anode-catalyzed oxidation remaining organic pollutant of degrading of electrolytic pole board be small organic molecule, while in electrolytic process in dope
Chloride ion to small organic molecule oxidative degradation and form carbon dioxide and water, water outlet after electrolysis returns to membrane biological reaction
Device, and the BOD/COD > 0.3 in water outlet carries out down pole after cell reaction slot runs 8~12h；
(6), tail gas absorption is handled: being taken out hydrogen, chlorine and carbon dioxide out of cell reaction slot by device for absorbing tail gas
Out, and micro-vacuum state in cell reaction slot is kept, it is up to standard after being absorbed with sodium hydrate aqueous solution to the chlorine in tail gas
Discharge.
The characteristics of present invention is for its COD of landfill leachate nanofiltration concentrate, total nitrogen and hardness ions excessive concentration, first leads to
Pressure nanofiltration film unit is handled in crossing, and middle pressure nanofiltration membrane component uses segmented inner circulation structure, can make dope cross-flow
Filter washes away to increase dope in the flow velocity of film surface and avoids pollution object in the accumulation of film surface, in addition in press nanofiltration membrane component
Operating pressure control in 10~20bar, so that middle pressure nanofiltration membrane component is run relatively stablely, reduction fouling membrane degree, pass through
Concentrated liquor of receiving after middle pressure nanofiltration membrane treatment can be reduced to 40~60%, realize decrement due to first passing through middle pressure nanofiltration membrane component
Change processing, therefore subsequent technique processing water can be reduced, reduce processing cost.After the present invention is using mixed condensed gas flotation process centering pressure nanofiltration
Dope be disposed, so that dope is generated the bubble adhesion of dispersion on metal salt and shape by air-dissolving air-float or air-dispersing air bearing
Pond body liquid level is swum at humus wadding body, the humus wadding body on pond body liquid level can not only be conveniently struck off, can remove in dope
45~60% organic matter solves in current coagulant sedimentation processing film-filter concentration liquid, because of coagulant and macromolecular humus shape
At wadding body precipitability it is poor, and the control of coagulation stirring intensity not at that time, make metallic salt wadding body can entrained air bubbles, precipitating
The problem of floating in pond, causing water outlet SS higher and treatment effect decline.The present invention is using resin sofening treatment to coagulation air-float
Treated, and dope is handled, can solve subsequent dope in electrolytic oxidation process electrolytic pole board be easy fouling the problem of, make
Water outlet that treated, which returns, not will cause hardness ions accumulation in membrane bioreactor, keep membrane bioreactor stable, and
Keep the efficiency of biological treatment system.The present invention uses electrolytic oxidation process dope, passes through cell reaction slot Inner electrolysis pole plate
Anode-catalyzed oxidation degrades residue organic pollutant as small organic molecule, while the chloride ion in electrolytic process in dope is to small
Molecular organic oxidative degradation simultaneously forms carbon dioxide and water, due to carrying out at normal temperatures and pressures, and using nanofiltration concentrate
Chloride ion in raw water is reacted, and is not needed to add oxidant and flocculant, is not generated secondary pollution, high treating effect.And
After at electrolytic oxidation, it is in water outlet and water outlet in BOD/COD > 0.3, enhance biodegradability.Method pair processed by the invention
After nanofiltration concentrate is handled outlet water organic substance concentration and total hardness concentration be below outlet water organic substance in membrane filtration clear liquid and
Total hardness concentration effectively avoids the accumulation of humus and hardness ions in membrane bioreactor, and small organic molecule can
It is removed by aeration tank in membrane bioreactor, since nitrogen pollutant is converted into nitrate nitrogen through oxidation, can return to membrane biological reaction
Denitrification disposition is carried out in device.Originally nanofiltration concentrate can be disposed into the acceptable degree of membrane bioreactor by entering invention, and will
Former percolation liquid treatment membrane is sent in the clear liquid of middle pressure nanofiltration, the water outlet of backwash water and alkaline chemical precipitation and the water outlet after electrolytic oxidation back to
Percolate raw water can be diluted in bioreactor, group technology high treating effect, investment and operating cost are lower.
Detailed description of the invention
The embodiment of the present invention is further described with reference to the accompanying drawing.
Fig. 1 is the flow chart of landfill leachate nanofiltration concentrate processing method of the present invention.
Fig. 2 is the structural schematic diagram of landfill leachate nanofiltration concentrate processing system of the present invention.
Fig. 3 is the structural schematic diagram of cell reaction slot of the present invention.
Fig. 4 is the sectional view of Fig. 3.
Wherein: 1-storage tank, 2-outlet tubes, 3-high-pressure pumps, 4-circulating pumps, 5-middle pressure nanofiltration membrane components, 6-controls
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-electrolytic cell, 12-2-electrolysis cycle pump, 12-3-partition, 12-4-anode plate, 12-5-cathode plate,
13-membrane bioreactors, 14-device for absorbing tail gas, 15-tracheaes, 16-intake pumps, 17-regenerated liquid pipes, 18-backwashes
Water treatment facilities, 19-pipelines, 20-dope pipes, 21-circulation pipes.
Specific embodiment
As shown in FIGS. 1 and 2 landfill leachate nanofiltration concentrate processing method of the invention, sequentially includes the following steps:
(1), middle pressure nanofiltration processing.
It is deposited using nanofiltration concentrate caused by MBR+NF method processing landfill leachate to can be carried out water quality and quantity in storage tank 1
It adjusts, hydrochloric acid is added into storage tank 1 or sulfuric acid is sufficiently stirred, the pH value of nanofiltration concentrate to be processed is adjusted to 6~6.5,
In order to postorder processing.As shown in Figure 2, storage tank 1 has inlet and liquid outlet, and blender is equipped in storage tank 1, and storage tank 1 goes out
Liquid mouth connect with the inlet of middle pressure nanofiltration membrane component 5 through outlet tube 2 and communicates, and high-pressure pump 3, nanofiltration are equipped on outlet tube 2
Concentrate in the feeding of high-pressure pump 3 through pressing in nanofiltration membrane component 5.It presses nanofiltration membrane component 5 to be that at least two-part is interior in the present invention to recycle
Structure, and the operating pressure of middle pressure nanofiltration membrane component 5, in 10~20bar, the operating pressure of such as middle pressure nanofiltration membrane component 5 exists
Existing rolling nanofiltration membrane can be used in 12bar or 15bar, middle pressure nanofiltration membrane component 5, and middle pressure nanofiltration membrane component 5 is two in concentrated water
Three stage structure in segmentation structure or concentrated water is pressed the membrane tube recycled in nanofiltration membrane element segments formula to be filtered processing, is pressed in
Mass percent, 10~20wt% dope is recycled through circulating pump 4, remaining dope is sent to coagulation floatation 7, and treated
Clear liquid returns to membrane bioreactor 13.As shown in Figure 2, the dope outlet of nanofiltration membrane component of the present invention is connected to dope pipe 20, dope
Pipe 20 is connect by three-way connection with circulation pipe 21 and pipeline 19, the other end and high-pressure pump 3 of the circulation pipe 21 equipped with circulating pump 4
The connection of outlet tube 2 behind outlet communicates the reflux that can carry out concentrated water, the pipeline 19 equipped with control valve 6 and coagulation air-float device 7
Inlet connection communicates, and the clear liquid mouth of nanofiltration membrane component 5 connects the inlet of membrane bioreactor 13, therefore energy by clear liquid pipe
Facilitate control liquid circulation amount by control valve 6, makes dope in membrane tube surface cross-flow filtration, can increase dope in the stream of film surface
Speed washes away and avoids pollution object in the accumulation of film surface.When the present invention uses 8 cun of nanofiltration membrane tubes, concentrate circulating amount is up to 15~
20m3/ h, by middle pressure nanofiltration, treated that dope is sent to coagulation floatation 7, receives concentrated liquor after pressing nanofiltration membrane treatment in
It can be reduced to 40~60%, clear liquid returns to membrane bioreactor 13 for diluting percolate raw water.Due to middle pressure nanofiltration clear liquid water
Matter is poor, and contained organic matter contaminant molecule amount is 300~600mg/L lower than 300, COD concentration, is far below percolate raw water
Middle pressure nanofiltration clear liquid is returned to MBR system, can dilute percolate raw water by COD value.
The present invention is sustainable to add film antisludging agent when middle pressure nanofiltration is handled, and film scale inhibitor dosing amount is 0.5~1L/h,
The present invention presses the operation of nanofiltration membrane component 5 12~primary with clear water wash cycles for 24 hours, when cleaning when middle pressure nanofiltration is handled in the middle
Between be 5~10 minutes, to be maintained in middle pressure nanofiltration membrane treatment process, can prevent contaminate object in film surface fouling.And it is received in middle pressure
Filter membrane component 5 is run every 6~12 months and is cleaned using chemical agent, is pressed in its membrane tube of nanofiltration membrane component 5 in elimination
Pollution, the permeant flux of nanofiltration membrane component 5 is pressed in holding.
(2), coagulation air-float is handled.
Coagulation floatation 7 is added after coagulant and flocculant are sufficiently mixed, or coagulation is added in coagulant and flocculant
Flotation tank 7 is sufficiently stirred, and by air-dissolving air-float or air-dispersing air bearing, dope is made to generate the bubble adhesion of dispersion on metal salt
And form humus wadding body and swim in pond body liquid level, coagulant of the present invention is metal salt, which can be used molysite or aluminium
Salt, such as ferric trichloride, ferrous sulfate hydrate and bodied ferric sulfate are used, dosage is 100~1000mg/L, and is wadded a quilt with cotton
Solidifying agent is organic polymer coargulator or microbial flocculant, and dosage is 1~2mg/L.The present invention can be used existing molten
Air flotation device or air-dispersing air-floating apparatus make the dope in coagulation floatation 7 generate the bubble adhesion of high degree of dispersion in metal salt
On, the humus wadding body on pond body liquid level is struck off by Slag Scraping Device and is recycled, humus a large amount of in dope are removed, and it is dense
Liquid is added in resin softening plant 9 by water inlet pipe 8, and the present invention is after coagulation air-float is handled, to organic matter in dope (COD)
Removal rate up to 45~60%, the humus sludge after striking off is collected, realize resource utilization.
(3), resin sofening treatment.
Coagulation air-float treated dope is sent into resin softening plant 9, as shown in Figure 2, that treated is dense for coagulation air-float
Liquid is added by water inlet pipe 8 to the top of resin softening plant 9, and the strong acid of 9 middle-jiao yang, function of the spleen and stomach ion-exchange area of resin softening plant is passed through
Property cation exchange resin softens dope, by the calcium ions and magnesium ions in dope in cationic exchange area with resin activity base
Ion-exchange reactions occurs for the exchangeable ion in group, is exchange product with hydrogen ion, the sodium ion in resin, softens through resin
Afterwards, make the total hardness removal rate > 60% in dope, 9 bottom of resin softening plant is equipped with water outlet, and resin softening plant 9 goes out
The mouth of a river is added in cell reaction slot 12 by outlet pipe 11 and intake pump 16.The present invention is using resin sofening treatment to coagulation air-float
Treated, and dope is handled, and can guarantee subsequent electrolytic oxidation section non flouling behaviour, and water outlet after processing returns to membrane bioreaction
It answers and not will cause hardness ions accumulation in device 13, solve the problem of that current membrane tube pressure rises system fluctuation of service.
(4), backwash water process.
After the storng-acid cation exchange resin saturation of resin softening plant 9, with the dilute hydrochloric acid of 3~5wt% to strong acid
Property cation exchange tree carry out backwash and regeneration, as shown in Figure 2, the dilute hydrochloric acid is by backwash water inlet pipe 10 from resin softening plant 9
Bottom enter, backwash and regeneration is carried out to strongly acidic cation exchange tree, the regeneration liquid waste that backwash generates is from resin softening plant 9
Top discharge, the regeneration liquid waste that backwash generates are entered in backwash water treatment facilities 18 by regenerated liquid pipe 17, backwash water process
Blender is equipped in device 18,18 bottom of backwash water treatment facilities is equipped with sludge outlet, the water outlet of backwash water treatment facilities 18
The inlet that membrane bioreactor 13 is connect by water pipe is handled regeneration liquid waste using alkaline chemical precipitation method, can be by regenerated
Liquid pH value is controlled 10~11, and the sludge after precipitating is carried out dehydrating, or by the biochemistry of sludge and percolation liquid treating system
Excess sludge mixing is carried out dehydrating, and the water outlet after alkaline chemical precipitation returns to membrane bioreactor 13.Lime can be used in the present invention
Method, lime-soda process or lime stone-gypsum method handle regeneration liquid waste, after being disposed by alkaline chemical precipitation method, effluent quality
In order, pollutant load is very low.
(5), electrolytic oxidation process.
Dope after softened is squeezed into cell reaction slot 12 by intake pump 16, the electrolytic pole board in cell reaction slot 12
Anode-catalyzed oxidation remaining organic pollutant of degrading be small organic molecule, while the chloride ion pair in electrolytic process in dope
Small organic molecule oxidative degradation simultaneously forms carbon dioxide and water, and the water outlet after electrolysis returns to membrane bioreactor 13, is being electrolysed
Reactive tank 12 carries out down pole after running 8~12h.Since to contain molecular weight lower for the dope after coagulation air-float and resin softening
Hardly degraded organic substance, the direct catalyzing and degrading pollutant of anode, electrolysis generates the indirect degradation of contaminant of strong oxidizer, i.e., using come dense
Hardly degraded organic substance direct oxidation is carbon dioxide and water and water outlet by the oxidisability of chloride ion electrolysate in liquid --- chlorine
In BOD/COD > 0.3, the biodegradability of waste water can be improved.
Its reaction process of electrolytic anode Direct Catalytic Oxidation of the present invention is as follows: reductive organic matter → small organic molecule+e~。
When the catalysis oxidation dominated with chloride, reaction process 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 slot 12 of the present invention is integrally closed structure, and cell reaction slot 12 has multiple only
Vertical and the electrolytic cell 12-1 communicated that is connected in series along liquid flow direction, the electrolytic cell 12-1 of front and last electrolytic cell 12-1 are logical
It crosses electrolysis cycle pump 12-2 connection to communicate, there are multiple concatenated electrolytic pole boards in each electrolytic cell 12-1, cell reaction slot 12
Liquid outlet is connect with the inlet of membrane bioreactor 13 by water pipe and is communicated, after 12 electrolytic oxidation process of cell reaction slot
Water outlet returns to membrane bioreactor 13 for diluting percolate raw water, and 12 top of cell reaction slot is inhaled by tracheae 15 and tail gas
The air inlet of receiving apparatus 14 connects.Since cell reaction slot 12 is integrally closed, only retain venthole, oxidation when electrolysis is generated
Hydrogen, chlorine and carbon dioxide be sucked out by device for absorbing tail gas 14.
As shown in Fig. 2~4, cell reaction slot 12 of the present invention is equipped at least two rows of electrolytic cell 12-1, and the electrolytic cell of front
12-1 is located at the same end and is connect by electrolysis cycle pump 12-2 with last electrolytic cell 12-1 to be communicated, to reduce space occupied,
The partition 12-3 of upper and lower misaligned interval is equipped in each electrolytic cell 12-1 along liquid flow direction, forms liquid in each electrolytic cell 12-1
The crossing type runner up and down that body passes through, and increase the flow channel length that dope passes through electrolytic cell 12-1, it can sufficiently carry out electrolytic oxidation
Processing.Electrolytic pole board in each electrolytic cell 12-1 of the present invention includes 20~50 anode plate 12-4 and corresponding 20~50 cathodes
Plate 12-5, and anode plate 12-4 has titanium-based ruthenium-oxide-oxidation iridium coating layer, cathode plate 12-5 uses stainless steel plate, such as uses
316L stainless steel plate, the spacing between anode plate 12-4 and cathode plate 12-5 is in 1~2cm.Anode plate 12-4 and cathode of the present invention
The specification of plate 12-5 is 0.3m × 0.8m, with a thickness of 1.5mm, by the DC voltage-stabilizing pulse power as power supply, work
When decomposition voltage be 10~30V, Faradaic current is 50~200A, and circular flow is 20~50 times of flow of inlet water, to guarantee
Electrolytically generated oxide is sufficiently mixed utilization.It is in room temperature that cell reaction slot 12 of the present invention, which carries out electrolytic oxidation process to dope,
It carries out under normal pressure, and is reacted using the chloride ion in nanofiltration concentrate raw water, do not need to add oxidant and flocculant, no
Secondary pollution can be generated.The present invention carries out down pole after electrolysis runs 8~12h, and the water outlet after electrolysis returns to film by return pipe
Bioreactor 13.
The present invention disposes nanofiltration concentrate to the acceptable degree of membrane bioreactor 13, press in the middle nanofiltration clear liquid,
The water outlet of backwash water process and the water outlet film feeding bioreactor 13 after electrolytic oxidation process are received with landfill leachate and carry out MBR
The processing of+NF method, after electrolytic oxidation, since the BOD/COD ratio of water outlet is promoted to 0.3 or more by 0.03, biodegradability enhances,
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
Denitrification pond is converted into nitrogen removal in membrane bioreactor 13, and it is tired in biochemical system to avoid humus and hardness ions
Product, high treating effect, investment and operating cost are lower.
(6), tail gas absorption is handled: by device for absorbing tail gas 14 by hydrogen, chlorine and carbon dioxide from cell reaction slot 12
Interior extraction, and micro-vacuum state in cell reaction slot 12 is kept, which can be used protected against explosion water injection vacuum
Unit, qualified discharge after being absorbed with sodium hydrate aqueous solution to the chlorine in tail gas, device for absorbing tail gas 14 of the present invention
Sodium hydrate aqueous solution is infused in water tank, sodium hydrate aqueous solution is the sodium hydrate aqueous solution of 10~40wt% concentration.It can determine
Phase detects the concentration of sodium hydrate aqueous solution, to guarantee assimilation effect.
Embodiment 1
Certain percolate from garbage filling field treatment plant treating capacity is 500m3/ d handles landfill leachate using MBR+NF method, produces
Raw 100m3/ d nanofiltration concentrate detects nanofiltration concentrate, COD in 3000mg/L, the ratio of BOD/COD 0.03, chlorine from
Son is in 6000mg/L, total hardness 7000mg/L, ammonia nitrogen 10mg/L, total nitrogen 300mg/L.
It is handled by landfill leachate nanofiltration concentrate processing method of the invention, nanofiltration concentrate is sent through high-pressure pump 3
Enter in pressure nanofiltration membrane component 5, nanofiltration processing is pressed in progress, the operating pressure of middle pressure nanofiltration membrane component 5 is in 15bar, producing water ratio
It is 50%, 4 flow of circulating pump is in 16m3/ h, middle pressure nanofiltration membrane component 5 is three stage structure in concentrated water, by nanofiltration concentrate pH value
It adjusts 6~6.5, using 8 cun of rolling nanofiltration membranes, 15wt% dope after processing is recycled, remaining is sent to coagulation floatation 7
Interior, nanofiltration water yield is 50m3/ d or so, operation 18h is primary with clear water wash cycles, and scavenging period is 6 minutes, and treated
It is 500mg/L that clear liquid, which returns to membrane bioreactor 13 for diluting percolate raw water, pressure nanofiltration clear liquid COD, and matter situation is superior to
Ultrafiltration clear liquid.
Nanofiltration is pressed in centering, and treated that dope is detected by GB16889-2008, and COD is in 5000mg/L, BOD/COD
Ratio 0.01, chloride ion is in 6000mg/L, and total hardness 8000mg/L, ammonia nitrogen is in 10mg/L, and total nitrogen is in 450mg/L.
By middle pressure nanofiltration, treated that dope is sent to coagulation floatation 7, after coagulant and flocculant are sufficiently mixed plus
Enter coagulation floatation 7, coagulant is molysite, can be used ferric trichloride, ferrous sulfate hydrate or bodied ferric sulfate wherein it
One or its mixing, dosage 500mg/L, flocculant be organic polymer coargulator or microbial flocculant, dosage
The humus wadding body on pond body liquid level is struck off with Slag Scraping Device, and will scrape after air-dissolving air-float or air-dispersing air bearing for 1.5mg/L
Humus sludge after removing is collected, and realizes resource utilization.To coagulation air-float treated water outlet detect, COD
In 2500mg/L, the ratio of BOD/COD is 0.03, and chloride ion is in 6200mg/L, total hardness 8000mg/L, ammonia nitrogen 10mg/L, always
Nitrogen 350mg/L.
By coagulation air-float treated water outlet be sent into resin softening plant 9 in, pass through the highly acid in resin softening plant 9
Cation exchange resin softens dope, detects to dope after softening, and COD is in 2500mg/L, the ratio of BOD/COD
Value is 0.03, and chloride ion is in 6200mg/L, and total hardness 2000mg/L, ammonia nitrogen is in 5mg/L, and total nitrogen is in 300mg/L.
After the storng-acid cation exchange resin saturation of resin softening plant 9, with the dilute hydrochloric acid of 3wt% to highly acid sun
Amberlite carries out backwash and regeneration, carries out alkaline chemical precipitation processing, and regeneration liquid waste pH value is controlled 10~11, after precipitating
Sludge is carried out dehydrating, or sludge is mixed with the biochemical excess sludge of percolation liquid treating system and is carried out dehydrating, water outlet
It returns in membrane bioreactor 13, treated that be discharged its COD be 100mg/L for backwash water, and water quality condition is superior to ultrafiltration clear liquid.
Dope after softened is squeezed into cell reaction slot 12 by intake pump 16, and electrolysis cycle pump 12-2 flow is
60m3There is 30 anode plate 12-4 and corresponding 30 cathode plate 12-5, anode plate 12-4 and yin in/h, each electrolytic cell 12-1
The specification of pole plate 12-5 is 0.3m × 0.8m, and with a thickness of 1.5mm, the spacing between anode plate 12-4 and cathode plate 12-5 is
1.5cm, decomposition voltage is 20V, Faradaic current 100A when work, carried out after electrolysis operation 10h it is extremely primary, to electrolytic oxidation
Treated, and water outlet is detected, and COD is in 500mg/L, and the ratio of BOD/COD is in > 0.03, and chloride ion is in 6000mg/L, always
Hardness 1500mg/L, for ammonia nitrogen in 5mg/L, water outlet of the total nitrogen after 300mg/L, electrolytic oxidation process returns to membrane bioreactor
13。
Hydrogen, chlorine and the carbon dioxide generated when electrolytic oxidation process passes through device for absorbing tail gas 14 from cell reaction slot
12 top extraction, qualified discharge after being absorbed with the sodium hydrate aqueous solution of 20wt% concentration to the chlorine in tail gas.
By the water outlet film feeding biology after the clear liquid, backwash water alkaline chemical precipitation water outlet water and electrolytic oxidation process of middle pressure nanofiltration
Reactor 13 and landfill leachate, which are received, carries out MBR+NF processing, after electrolytic oxidation, since the BOD/COD ratio of water outlet is by 0.03
It is promoted to 0.3 or more, biodegradability enhances, and the small organic molecule in water outlet can be gone by aeration tank in membrane bioreactor 13
It removes, the nitrate nitrogen in electrolysis water outlet then passes through denitrification pond in membrane bioreactor 13 and is converted into nitrogen removal.It is obtained to after processing
To clear liquid detected, COD can meet GB16889- in 30mg/L, water outlet in 5mg/L, total nitrogen in 80mg/L, ammonia nitrogen
2008 table, 2 discharge standard.
Embodiment 2
It is handled by landfill leachate nanofiltration concentrate processing method of the invention, nanofiltration concentrate is sent through high-pressure pump 3
Enter in pressure nanofiltration membrane component 5, nanofiltration processing is pressed in progress, the operating pressure of middle pressure nanofiltration membrane component 5 is in 20bar, producing water ratio
It is 55%, 4 flow of circulating pump is in 20m3/ h, two-period form structure in middle 5 concentrated water of pressure nanofiltration membrane component, by nanofiltration concentrate pH value tune
Section, using 8 cun of rolling nanofiltration membranes, 18wt% dope after processing is recycled, remaining is sent to coagulation floatation 7 6~6.5
It is interior, film antisludging agent is persistently added, film scale inhibitor dosing amount is 0.8L/h, and middle pressure nanofiltration water yield is 50m3/ d or so runs 20h
Primary with clear water wash cycles, scavenging period is 8 minutes, and treated, and clear liquid returns to membrane bioreactor 13 for diluting diafiltration
Liquid raw water, middle pressure nanofiltration clear liquid COD are 300mg/L, and matter situation is superior to ultrafiltration clear liquid.
Nanofiltration is pressed in centering, and treated that concentrate is detected by GB16889-2008, and COD is in 5500mg/L, BOD/
The ratio of COD is 0.01, and chloride ion is in 6000mg/L, and total hardness 8000mg/L, ammonia nitrogen is in 10mg/L, and total nitrogen is in 450mg/L.
By middle pressure nanofiltration, treated that dope is sent to coagulation floatation 7, after coagulant and flocculant are sufficiently mixed plus
Enter coagulation floatation 7, coagulant is molysite, can be used ferric trichloride, ferrous sulfate hydrate or bodied ferric sulfate wherein it
One or its mixing, dosage 800mg/L, flocculant be organic polymer coargulator or microbial flocculant, dosage
For 1.5mg/L；After air-dissolving air-float or air-dispersing air bearing, the humus wadding body on pond body liquid level is struck off with Slag Scraping Device, and will scrape
Humus sludge after removing is collected, and realizes resource utilization.And to coagulation air-float treated water outlet detect,
COD in 2200mg/L, the ratio of BOD/COD 0.03, chloride ion in 6200mg/L, total hardness 8000mg/L, ammonia nitrogen 10mg/L,
Total nitrogen 350mg/L.
Coagulation air-float treated dope is sent into resin softening plant 9, passes through the highly acid sun in resin softening plant 9
Ion exchange resin softens dope, detects to dope after softening, and COD is in 2200mg/L, the ratio of BOD/COD
0.03, chloride ion is in 6200mg/L, and total hardness 1000mg/L, ammonia nitrogen is in 5mg/L, and total nitrogen is in 300mg/L.
After the storng-acid cation exchange resin saturation of resin softening plant 9, with the dilute hydrochloric acid of 5wt% to highly acid sun
Amberlite carries out backwash and regeneration, and regeneration liquid waste pH value is controlled 10~11, is dehydrated to the sludge after alkaline chemical precipitation
Processing, or sludge is mixed with the biochemical excess sludge of percolation liquid treating system and is carried out dehydrating, water outlet returns to membrane bioreaction
It answers in device 13, treated that be discharged its COD be 100mg/L for backwash water, and water quality condition is superior to ultrafiltration clear liquid.
Dope after softened is squeezed into cell reaction slot 12 by intake pump 16, and electrolysis cycle pump 12-2 flow is
80m3There is 40 anode plate 12-4 and corresponding 40 cathode plate 12-5, anode plate 12-4 and yin in/h, each electrolytic cell 12-1
The specification of pole plate 12-5 is 0.3m × 0.8m, and with a thickness of 1.5mm, the spacing between anode plate 12-4 and cathode plate 12-5 is
1.5cm, decomposition voltage is 20V, Faradaic current 100A when work, carried out after electrolysis operation 10h it is extremely primary, to electrolytic oxidation
Treated, and water outlet is detected, and COD is in 400mg/L, and the ratio of BOD/COD is in > 0.03, and chloride ion is in 6000mg/L, always firmly
800mg/L is spent, for ammonia nitrogen in 5mg/L, water outlet of the total nitrogen after 300mg/L, electrolytic oxidation process is logical to return to membrane bioreactor 13.
Hydrogen, chlorine and the carbon dioxide that electrolytic oxidation process generates pass through device for absorbing tail gas 14 from cell reaction slot 12
Top extraction, qualified discharge after being absorbed with the sodium hydrate aqueous solution of 30wt% concentration to the chlorine in tail gas.
By the middle pressure clear liquid of nanofiltration, backwash water process water outlet and electrolytic oxidation process after water outlet film feeding biological respinse
Device 13 and landfill leachate, which are received, carries out the processing of MBR+NF method, after electrolytic oxidation, since the BOD/COD ratio of water outlet is mentioned by 0.03
0.3 or more is risen to, biodegradability enhances, and the small organic molecule in water outlet can be gone by aeration tank in membrane bioreactor 13
It removes, the nitrate nitrogen in electrolysis water outlet then passes through denitrification pond in membrane bioreactor 13 and is converted into nitrogen removal.To treated
Clear liquid is detected, and COD can meet GB16889-2008 table 2 in 30mg/L, water outlet in 5mg/L, total nitrogen in 80mg/L, ammonia nitrogen
Discharge standard can enable former percolation liquid treatment membrane bio-reaction system stable operation.
Claims (9)
1. a kind of landfill leachate nanofiltration concentrate processing method, it is characterised in that: it carries out according to the following steps,
(1), middle pressure nanofiltration processing: the pH value of nanofiltration concentrate to be processed is controlled 6~6.5, by nanofiltration concentrate through high-pressure pump
It is pressed in nanofiltration membrane component in feeding, the middle pressure nanofiltration membrane component is at least two-part inner circulation structure, and middle pressure nanofiltration membrane
The operating pressure of element is in 10~20bar, after the membrane tube filtration treatment recycled in nanofiltration membrane element segments formula is pressed in, by 10~
The dope of 20wt% is recycled through circulating pump, remaining dope is sent to coagulation floatation, and treated, and clear liquid returns to film biology
Reactor；
(2), coagulation air-float is handled: being added coagulation floatation after coagulant and flocculant are sufficiently mixed, or by coagulant and flocculation
Agent is added coagulation floatation and is sufficiently stirred, and by air-dissolving air-float or air-dispersing air bearing, dope is made to generate the bubble adhesion of dispersion
It on metal salt and forms humus wadding body and swims in pond body liquid level, strike off the humus wadding body on pond body liquid level and recycle benefit
With wherein the coagulant is metal salt, dosage is 100~1000mg/L, and the flocculant is organic polymer wadding
Solidifying agent or microbial flocculant, dosage are 1~2mg/L；
(3), resin sofening treatment: coagulation air-float treated dope is sent into resin softening plant, resin softening plant is passed through
The storng-acid cation exchange resin of middle-jiao yang, function of the spleen and stomach ion-exchange area softens dope, by the calcium ions and magnesium ions in dope in exchange area
Ion-exchange reactions, and the total hardness removal rate > 60% in dope occur for the interior exchangeable ion with resin activity group；
(4), backwash water process: after the storng-acid cation exchange resin saturation of resin softening plant, with 3wt%~5wt%'s
Dilute hydrochloric acid carries out backwash and regeneration to storng-acid cation exchange resin, and the regeneration liquid waste that backwash generates enters backwash water treatment facilities
In, it is handled with alkaline chemical precipitation method, the sludge after precipitating is carried out dehydrating, the water outlet after alkaline chemical precipitation returns to membrane biological reaction
Device；
(5), electrolytic oxidation process: the dope after softened is squeezed into cell reaction slot by intake pump, the electricity in cell reaction slot
The anode-catalyzed oxidation for solving pole plate degrades residue organic pollutant as small organic molecule, while the chlorine in electrolytic process in dope
The oxidative degradation of ion pair small organic molecule simultaneously forms carbon dioxide and water, and the water outlet after electrolysis returns to membrane bioreactor, and
BOD/COD > 0.3 in water outlet carries out down pole after cell reaction slot runs 8~12h；
(6), tail gas absorption is handled: hydrogen, chlorine and carbon dioxide are extracted out out of cell reaction slot by device for absorbing tail gas,
And micro-vacuum state in cell reaction slot is kept, row up to standard after being absorbed with sodium hydrate aqueous solution to the chlorine in tail gas
It puts.
2. landfill leachate nanofiltration concentrate processing method according to claim 1, it is characterised in that: received in medium pressure
When filter processing, film antisludging agent is persistently added, and film scale inhibitor dosing amount is 0.5~1L/h.
3. landfill leachate nanofiltration concentrate processing method according to claim 1, it is characterised in that: received in medium pressure
When filter processing, nanofiltration membrane component operation 12~primary with pressure nanofiltration membrane component in clear water wash cycles for 24 hours, scavenging period is pressed in the middle
It is 5~10 minutes.
4. landfill leachate nanofiltration concentrate processing method according to claim 1, it is characterised in that: received in medium pressure
When filter processing, presses nanofiltration membrane component to run in the middle every 6~12 months and cleaned using chemical agent, to eliminate the dirt in membrane tube
Dye.
5. landfill leachate nanofiltration concentrate processing method according to claim 1, it is characterised in that: in the coagulation gas
After floating processing, the COD removal rate in dope is 45~60%.
6. landfill leachate nanofiltration concentrate processing method according to claim 1, it is characterised in that: inhaled in the tail gas
Receipts processing, sodium hydrate aqueous solution are the sodium hydrate aqueous solution of 10~40wt% concentration.
7. landfill leachate nanofiltration concentrate processing method according to claim 1, it is characterised in that: the electrolysis is anti-
Answering slot is integrally closed structure, and cell reaction slot has multiple independent and electrolytic cells communicated that are connected in series along liquid flow direction,
And the electrolytic cell of front is communicated with last electrolytic cell by electrolysis cycle pump connection, has multiple concatenated electrolysis in each electrolytic cell
The liquid outlet of pole plate, cell reaction slot is communicated by water pipe with the connection of the inlet of membrane bioreactor, cell reaction slot top
It is connected by the air inlet of tracheae and device for absorbing tail gas.
8. landfill leachate nanofiltration concentrate processing method according to claim 1, it is characterised in that: each electrolytic cell
The interior partition that upper and lower misaligned interval is equipped with along liquid flow direction, the interior crossing type stream up and down passed through with liquid of each electrolytic cell
Road.
9. landfill leachate nanofiltration concentrate processing method according to claim 1, it is characterised in that: each electrolytic cell
Interior electrolytic pole board includes 20~50 anode plates and corresponding 20~50 cathode plates, and anode plate has titanium-based ruthenium-oxide-
Iridium coating layer is aoxidized, cathode plate uses stainless steel plate, and the spacing between anode plate and cathode plate is in 1~2cm.
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| CN109081522B (en) * | 2018-09-21 | 2023-09-19 | 桂润环境科技股份有限公司 | Treatment device and method for landfill leachate of household garbage landfill |
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