CN107265764A - Landfill leachate treatment is to its in line method up to standard - Google Patents

Landfill leachate treatment is to its in line method up to standard Download PDF

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CN107265764A
CN107265764A CN201710528225.8A CN201710528225A CN107265764A CN 107265764 A CN107265764 A CN 107265764A CN 201710528225 A CN201710528225 A CN 201710528225A CN 107265764 A CN107265764 A CN 107265764A
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catalytic
standard
percolate
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aerobic
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CN107265764B (en
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代春龙
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Shandong Longantai Environmental Protection Sci-Tech Co Ltd
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Shandong Longantai Environmental Protection Sci-Tech Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/06—Contaminated groundwater or leachate
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/30—Aerobic and anaerobic processes

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

The invention belongs to technical field of waste water processing, and in particular to a kind of percolate in line processing method up to standard.Landfill leachate treatment is to its in line method up to standard, including following steps：Anaerobic bio-treated --- Aerobic biological process --- iron-carbon micro-electrolysis --- Fenton oxidation --- catalytic ozonation --- catalytic and oxidative electrolysis technology.Percolate is handled using the method for the present invention, national regulations are reached, deep to wastewater treatment, operation is flexible, and anti-water impact capacity is strong, and processing cost is low.The present invention first removes most of organic matter and total nitrogen using the low bioanalysis of processing cost, rail carbon micro-electrolytic processes remove remainder organic matter, then hydrogen peroxide is added, Fenton oxidation, catalysis oxidation is carried out using electrode coating, current density between reduction pole plate, saves power consumption, reduces processing cost while treatment effect is ensured.

Description

Landfill leachate treatment is to its in line method up to standard
Technical field
The invention belongs to technical field of waste water processing, and in particular to a kind of percolate in line processing method up to standard.
Background technology
Percolate be garbage loading embeading processing after, due to the immersion of the leaching and surface water, underground water of Atmospheric precipitation, Gu Body discarded object is under physics, chemistry and microbial action, the high concentrated organic wastewater of generation.The generation of percolate comes from three Individual aspect:One is atmospheric precipitation (snow), rainwash and underground water invasion；Two be original moisture in rubbish；Three be that rubbish is filled out The organic wastewater produced after burying due to microbiological anaerobic decomposition.Pollutant in percolate essentially from：Rubbish The great amount of soluble organic matter and inorganic matter itself contained；Dissolved during the immersion of rainwater, surface water or underground water and Into the organic matter and inorganic matter of percolate；Solable matter and earthing that rubbish is produced by biology, physics, chemical action With the solable matter for entering percolate in surrounding soil.Percolate is as high concentrated organic wastewater, if unprocessed straight Run in and put, serious pollution can be caused to the underground water around landfill yard, surface water and soil.
Because percolate water quality is complicated and changes greatly, the features such as with biological toxic action, for garbage filter The treatment technology of liquid is always the focus of educational circles's research, because percolate composition is extremely complex, is handled very with a kind of method It is difficult up to standard, frequently with a variety of different type process integrations using just effluent quality being made to reach national row in general Practical Project Put standard.At this stage, the main refuse leachate treatment technology of China has traditional physico-chemical process and bioanalysis, and film A variety of processing modes such as processing method, land law.
With difference of the modern industry according to discharge standard, the typical two stage treatment of percolate typically need to be by pre- place The processes such as reason, anaerobism and aerobic biological treatment, wherein Aerobic Process for Treatment can select to coordinate with ultrafiltration, form MBR techniques.For up to To higher emission request or reuse requirement, MBR water outlets typically carry out tertiary treatment using nanofiltration+reverse osmosis process.By three Percolate after level processing can reach the requirement of recycle-water, but in tertiary treatment processes double membrane process can all produce it is dense Water, reverse osmosis concentrated water can return to nanofiltration front end and be intake as nanofiltration, and nanofiltration concentrated water have accumulated dense all kinds of salinities and Organic matter, there is no cost-effective processing means to handle it now, typically cause rubbish to ooze to refuse landfill its recharge Filtrate salinity and hardly degraded organic substance concentration more and more higher, cause original processing system to be paralysed.
The content of the invention
In order to solve above-mentioned technical problem, the present invention is for existing process to the deficiency during landfill leachate treatment Part utilizes hypoxic-ischemic brain-damage+aerobe filter there is provided a kind of percolate in line processing method up to standard, the invention Pond+iron-carbon micro-electrolysis+Fenton oxidation+catalytic ozonation+catalytic and oxidative electrolysis technology group technology is handled percolate, Make the direct qualified discharge of the percolate after processing.
The percolate in line processing method up to standard of the present invention is to solve the above by following technical schemes Technical problem：
Landfill leachate treatment is to its in line method up to standard, including following steps：
Anaerobic bio-treated --- Aerobic biological process --- iron-carbon micro-electrolysis --- Fenton oxidation --- ozone catalytic oxygen Change --- catalytic and oxidative electrolysis technology.
More specifically, landfill leachate treatment of the invention is to its in line method up to standard, including following steps：
（1）Anaerobe is handled：
Percolate hydraulic retention in anoxic biological tank；
Dissolved oxygen in anoxic biological tank is controlled in below 0.5mg/L, pH value is 6-9；
Muddy water mixing uses mechanical agitation in anoxic biological tank；
（2）Aerobic microbiological processing：
Semi-soft biologic packing material is hung in aerobic biofilter, the packing volume ratio of the biologic packing material is 30-70%；
Percolate hydraulic retention in aerobic filter tank；
Dissolved oxygen in aerobic filter tank is controlled in 2.0-6.0mg/L；
The return sludge ratio that anoxic biological tank is back in aerobic filter tank is 100-400%；
(3) iron-carbon micro-electrolysis
Water inlet uses inorganic acid for adjusting pH value, and it is 2.0-3.0 to control inlet flow-patterm, and water outlet pH is 3.0-4.0；
In the step, using solid packing, light electrolysis oxidization time is 15-120 minutes；
（4）Fenton oxidation：
The hydrogen peroxide that mass concentration is 30% is added, the volume that hydrogen peroxide is added is percolate volume for 0.5-10 ‰；
Oxidization time is 15-60 minutes；
Fenton water outlet pH adds alkali to pull back to pH8.0-9.0；
（5）Catalytic ozonation：
Ozone used catalyst is added in catalytic ozonation reactor；
Ozone dosage is 25-200mg/L；
The ozone oxidation time is 30-120 minutes；
（6）Catalytic and oxidative electrolysis technology
The catalysis oxidation in catalytic and oxidative electrolysis technology reactor；In catalytic and oxidative electrolysis technology reactor parallel arranged at least one set anode, The pole plate that negative electrode is alternately arranged；
Current density is 5.0-20mA/cm between pole plate, and pole plate spacing is 1-5cm；
Oxidization time is 30-120 minutes.
As a modification of the present invention, the present invention is improved on filler, is specially：
Step（3）In, the packing material size used is 3-10cm, in the filler, and the mass fraction of iron powder is 68-72%, carbon dust Mass fraction is 15-22%, and Cu, Mn, Ti, Pd mol ratio are（1-3）:（0.5-1.5）: (0.5-1.5): (0.2-0.8)； By above-mentioned raw material mixed-forming, formed through 1200-1500 DEG C of anoxybiotic high temperature sintering.
It is preferred that, step（3）In, the packing material size used is 3-10cm, in the filler, and the mass fraction of iron powder is 70%, the mass fraction of carbon dust is 20%, and Cu, Mn, Ti, Pd mol ratio are 2:1:1:0.5；By above-mentioned raw material mixed-forming, Formed through 1200-1500 DEG C of anoxybiotic high temperature sintering.
It is used as another improvement of the present invention, step（5）In, the catalyst used in ozone is improved, used in the ozone Catalyst is with TiO2-Al2O3Composite is carrier, by containing Mn2+、Cu2+、Fe3+、Ce3+、Co2+Concentration ratio is (0.8- 1.2):( 0.8-1.2): (0.8-1.2):( 0.8-1.2):The mixed liquor of (0.3-0.6), is stirred at room temperature dipping 4h, mistake After filter washing, obtained ozone used catalyst is dried into 2h at 120 DEG C, is then calcined and is prepared from 300 DEG C.
It is preferred that, step（5）In, ozone used catalyst is with TiO2-Al2O3Composite is carrier, by containing Mn2+、 Cu2+、Fe3+、Ce3+、Co2+Concentration ratio is 1:1:1:1:0.5 mixed liquor, is stirred at room temperature after dipping 4h, filtration washing, will Obtained ozone used catalyst dries 2h at 120 DEG C, is then calcined and is prepared from 300 DEG C.
Parallel arranged at least one set positive and negative pole in catalytic and oxidative electrolysis technology reactor, positive and negative pole is alternately arranged；Anode is certainly Ti-based coating electrode processed, coating material is the PbO of Eu, Nd, Pt codope2；Negative electricity extremely stainless steel electrode or graphite electrode；
Current density is 5.0-20mA/cm between pole plate, and pole plate spacing is 1-5cm；Oxidization time is 30-120 minutes.
Step（2）In, semi-soft biologic packing material is efficient inner support hanging filler, and this filler is used as surface material using cotton fiber Material, interior to be stock using PVC be composed in series as support, and with cordage.
In more detail, landfill leachate treatment of the invention is to its in line method up to standard, including following steps：
（1）Anaerobic bio-treated：
Hydraulic detention time of the percolate in anoxic biological tank is 10-50 hours；
Keep sludge concentration 3000-9000mg/L in anoxic pond；
Dissolved oxygen in anoxic pond is controlled in below 0.5mg/L, and pH value is 6-9；
Anoxic pond muddy water hybrid mode uses mechanical agitation under liquid；
（2）Semi-soft biologic packing material is hung in aerobic biofilter, described biologic packing material packing volume ratio is 30-70%；
Hydraulic detention time of the percolate in aerobic filter tank is 10-50 hours；
Suspended sludge concentration 2000-5000mg/L in aerobic filter tank；
Dissolved oxygen in aerobic filter tank is controlled in 2.0-6.0mg/L；
The return sludge ratio that anoxic biological tank is back in aerobic filter tank is 100-400%.
(3) iron-carbon micro-electrolysis
Water inlet carries out pH regulations using sulfuric acid or hydrochloric acid, and it is 2.0-3.0 to control inlet flow-patterm, and water outlet pH is 3.0-4.0；
In the step, using solid packing, packing material size is 3-10cm；In the filler, the mass fraction of iron powder is 68-72%, carbon The mass fraction of powder is 15-22%, and Cu, Mn, Ti, Pd mol ratio are（1-3）:（0.5-1.5）: (0.5-1.5): (0.2- 0.8)；By above-mentioned raw material mixed-forming, formed through 1200-1500 DEG C of anoxybiotic high temperature sintering；
Light electrolysis oxidization time is 15-120 minutes；
（4）Fenton oxidation：
The hydrogen peroxide that mass concentration is 30% is added, the volume that hydrogen peroxide is added is percolate volume for 0.5-10 ‰；
Oxidization time is 15-60 minutes；
Fenton water outlet pH adds alkali to pull back to 8.0-9.0；
（5）Catalytic ozonation：
Catalytic ozonation reactor is tower structure, wherein being filled with ozone used catalyst, ozone used catalyst is with TiO2- Al2O3Composite is carrier, by containing Mn2+、Cu2+、Fe3+、Ce3+、Co2+Concentration ratio is (0.8-1.2):( 0.8-1.2): (0.8-1.2):( 0.8-1.2):The mixed liquor of (0.3-0.6), is stirred at room temperature after dipping 4h, filtration washing, by what is obtained Catalyst dries 2h at 120 DEG C, is then calcined and is prepared from 300 DEG C；
Ozone dosage is 25-200mg/L；
The ozone oxidation time is 30-120 minutes；
（6）Catalytic and oxidative electrolysis technology
Catalytic and oxidative electrolysis technology reactor is at least one set of positive and negative pole of parallel arranged, positive and negative pole alternating in square structure, reactor Arrangement, anode is ti-based coating electrode, and coating material is PbO2、IrO2、TaO2At least one of；Negative electricity extremely stainless steel electricity Pole or graphite electrode；
Current density is 5.0-20mA/cm between pole plate, and pole plate spacing is 1-5cm；
Oxidization time is 30-120 minutes.
The beneficial effects of the present invention are：
（1）Reach national regulations
Rubbish infiltration filter is handled by the method for the present invention, its treatment effect can reach《Consumer waste filling and embedding pollution control Standard processed》In GB16889-2008 to COD in percolate, ammonia nitrogen, total nitrogen index the requirement of concentration of emission limit value；
（2）It is deep to wastewater treatment
Organic matter complexity in waste water is various, and its oxidation resistance is strong and weak different, using anoxic biological tank+aerobic biofilter+ Iron-carbon micro-electrolysis+Fenton oxidation+catalytic ozonation+catalytic and oxidative electrolysis technology is handled useless Organic substance in water " classifying successively ", is carried High wastewater treatment depth；
（3）Operation is flexible, and anti-water impact capacity is strong
Can be according to pending waste water quality flexible operating each unit technological parameter, to ensure stable water outlet qualified discharge；
（4）Processing cost is low
Most of organic matter and total nitrogen are first removed using the low bioanalysis of processing cost, rail carbon micro-electrolytic processes remove remainder Organic matter, then adds hydrogen peroxide, and the ferrous ion produced using iron-carbon micro-electrolysis unit is catalyst, and utilizes light electrolysis list The acidity of member carries out Fenton oxidation, compared with traditional Fenton oxidation, without acid adding and plus ferrous salt；Catalytic ozonation is then utilized The catalytic action of catalyst reduces ozone dosage while treatment effect is improved；Catalytic and oxidative electrolysis technology unit then make use of electricity Pole coating carries out catalysis oxidation, and current density between reduction pole plate, saves power consumption while treatment effect is ensured, so a whole set of work Skill processing cost is low.
Brief description of the drawings
Fig. 1 is a kind of percolate in line processing method process chart up to standard of the present invention；
Fig. 2 is the structural representation of electrolytic catalysis oxygen reactor；
In figure：1- anoxic biological tanks；2- aerobic biofilters；3- biochemical sedimentation basins；4- iron-carbon micro-electrolysis pond；5- Fenton oxidations Pond；6- flocculation sedimentation tanks；7- catalytic ozonation reactors；8- catalytic and oxidative electrolysis technology reactors.
Embodiment
Come to be further described the present invention with reference to the accompanying drawings and detailed description, so as to the technology of this area Personnel know more about the present invention, but do not limit the present invention with this.
The present invention technological process approximately as：
A kind of processing method of percolate, as shown in Figure 1, method of the invention is come pair by the following means for technological process Percolate is handled：
Pending percolate initially enters anoxic biological tank 1, and it is 3000-9000mg/L to keep sludge concentration in anoxic biological tank 1, Dissolved oxygen control is 6-9 in below 0.5mg/L, pH value control, and muddy water hybrid mode uses mechanical agitation under liquid, during hydraulic retention Between be 10-50 hour, nitrate in water is converted into nitrogen spilling by denitrifying bacterium under anoxic conditions, and anoxic biological tank 1 goes out Water enters aerobic biofilter 2；
Semi-soft biologic packing material is hung in aerobic biofilter 2, the semi-soft biologic packing material of the above is inner support hanging filler, this Filler is using cotton fiber as surfacing, and interior to be stock using PVC be composed in series as support, and with cordage（Such as without spy It is disclosed as described above on semi-soft biologic packing material in different explanation, following examples）；Biologic packing material packing volume ratio For 30-70%；It is 2000-5000mg/L to keep suspended sludge concentration in aerobic filter tank 2, and dissolved oxygen is in 2.0-6.0mg/L, pH value For 6-9, hydraulic detention time is 10-50 hours, and partial organic substances and ammonia nitrogen are divided by the aerobic microbiological for being attached to carrier in water Solve as CO2、H2O、NO3 2-, the water part of aerobic biofilter 2 is back to anoxic biological tank 1 by reflux ratio 100-400% and removed NO3 2-, the water outlet of aerobic biofilter 2, which enters in biochemical sedimentation basin 3, carries out mud-water separation, and base sludge is back to anoxic biological tank 1, supernatant adjusts pH to 2.0-3.0 by acid adding the Primary Oxidation in the electrolysis step for carrying out iron-carbon micro-electrolysis pond 4；
In the electrolysis step in iron-carbon micro-electrolysis pond 4, light electrolysis oxidation reaction 15-120 minutes, acid adding controls water outlet in course of reaction Water outlet addition 0.5-10 ‰ hydrogen peroxide enters Fenton oxidation after pH 3.0-4.0, iron-carbon micro-electrolysis oxidation removal partial organic substances Pond 5 carries out secondary oxidation (mass concentration of hydrogen peroxide is 30%)；In the step, using solid packing, packing material size is 3- 10cm；In the filler, the mass fraction of iron powder is 68-72%, and the mass fraction of carbon dust is 15-22%, Cu, Mn, Ti, Pd mole Than for（1-3）:（0.5-1.5）: (0.5-1.5): (0.2-0.8)；By above-mentioned raw material mixed-forming, through 1200-1500 DEG C Anoxybiotic high temperature sintering is formed；
Oxidization time of the waste water in Fenton oxidation pond 5 is 15-60 minutes, adds the hydrogen peroxide that mass concentration is 30%, hydrogen peroxide The volume of addition is percolate volume for 0.5-10 ‰；
Enter ferric ion in flocculation sedimentation tank 6, waste water after Fenton oxidation water outlet addition alkali lye readjustment pH to 8.0-9.0 to be formed Iron hydroxide flco is precipitated, and the bottom of sediment autoflocculation sedimentation basin 6 discharge, supernatant enters catalytic ozonation reactor 7, In catalytic ozonation reactor 7, waste water and 25-200mg/L ozone enter from the bottom of catalytic ozonation reactor 7, Three oxidations are carried out under the catalytic action of catalyst in catalytic ozonation reactor 7, oxidation enters electricity after 30-120 minutes Solve in catalytic oxidizer 8；
Catalytic ozonation reactor 7 is tower structure, wherein the ozone used catalyst being filled with, is with TiO2-Al2O3It is compound Material is carrier, by containing Mn2+、Cu2+、Fe3+、Ce3+、Co2+Concentration ratio is (0.8-1.2):( 0.8-1.2): (0.8- 1.2):( 0.8-1.2):The mixed liquor of (0.3-0.6), is stirred at room temperature after dipping 4h, filtration washing, by obtained catalysis 2h is dried in agent at 120 DEG C, is then calcined and is prepared from 300 DEG C；
In catalytic and oxidative electrolysis technology reactor 8, four oxidations, pole plate spacing 1-5cm, electric current are carried out in the presence of applying direct current Density 5-20 mA/cm, useless chlorion of Organic substance in water while catalyticing anode is aoxidized in water is electrolysed as hypochlorous acid, secondary Chloric acid is aoxidized to the ammonia nitrogen in waste water, row up to standard after waste water is aoxidized 30-120 minutes in catalytic and oxidative electrolysis technology reactor 8 Put.
Catalytic and oxidative electrolysis technology reactor 8 is square structure（As shown in Figure 2）, it is parallel in catalytic and oxidative electrolysis technology reactor 8 At least one set of positive and negative pole of arrangement, positive and negative pole is alternately arranged, and anode is ti-based coating electrode, and coating material is PbO2、IrO2、 TaO2At least one of；Negative electricity extremely stainless steel electrode or graphite electrode.Current density is 5.0-20mA/cm, pole between pole plate Plate spacing is 1-5cm；
Oxidization time is 30-120 minutes.
Below according to described above, select typical industrial wastewater to deal with objects, carry out specific implementation explanation.
Embodiment 1
The percolate produced during certain garbage burning factory dumping：After testing, COD is 13600mg/L in the percolate, Ammonia nitrogen is 1800mg/L, and nitrate is 210mg/L, and total nitrogen is 2500mg/L.
The processing method provided using the present invention is handled：
Pending percolate initially enters anoxic biological tank 1, and it is 9000mg/L, dissolving to keep sludge concentration in anoxic biological tank 1 Oxygen is in 0.2mg/L, and pH value is 6, and muddy water hybrid mode uses mechanical agitation under liquid, and hydraulic detention time is 50 hours, anoxic life The water outlet of thing pond 1 enters aerobic biofilter 2；
Semi-soft biologic packing material is hung in aerobic biofilter 2, the packing volume ratio of the biologic packing material is 40%；Keep aerobic life Suspended sludge concentration is 5000mg/L in thing filter tank 2, and dissolved oxygen is in 6.0mg/L, and pH value is 9, and hydraulic detention time is 50 hours, Partial organic substances and ammonia nitrogen are decomposed into CO by the aerobic microbiological for being attached to carrier in water2、H2O、NO3 2-, aerobic biofilter 2 goes out Water section is back to anoxic biological tank 1 by reflux ratio 400% and removes NO3 2-, the water outlet of aerobic biofilter 2 enter biochemical sedimentation basin 3 Middle carry out mud-water separation, base sludge is back to anoxic biological tank 1, and supernatant is adjusted pH to entering iron after 2.0 by acid adding Primary Oxidation is carried out in carbon micro-electrolysis pond 4；During iron-carbon micro-electrolysis, oxidation reaction 120 minutes, acid adding controls water outlet in course of reaction The hydrogen peroxide of water outlet addition 10 ‰ is carried out into Fenton oxidation pond 5 after pH 4.0, iron-carbon micro-electrolysis oxidation removal partial organic substances Secondary oxidation；
In the step, using solid packing, packing material size is 3-10cm；In the filler, the mass fraction of iron powder is 70% or so, The mass fraction of carbon dust is 20% or so, and Cu, Mn, Ti, Pd mol ratio are 2:1: 1: 0.5；Above-mentioned raw material is mixed into Type, is formed through 1200-1500 DEG C of anoxybiotic high temperature sintering；
Oxidization time of the waste water in Fenton oxidation pond 5 is 60 minutes, and it is laggard that Fenton oxidation water outlet adds alkali lye readjustment pH to 9.0 Enter ferric ion formation iron hydroxide flco precipitation in flocculation sedimentation tank 6, waste water, the bottom of sediment autoflocculation sedimentation basin 6 row Go out, supernatant enters catalytic ozonation reactor 7；
In catalytic ozonation reactor 7, waste water and 200mg/L ozone enter from the bottom of catalytic ozonation reactor 7, In catalytic ozonation reactor 7 under the catalytic action of ozone used catalyst carry out three times oxidation, oxidation 120 minutes it is laggard Enter catalytic and oxidative electrolysis technology reactor 8, four oxidations, pole plate spacing 1cm, current density are carried out in the presence of applying direct current 20mA/cm, useless chlorion of Organic substance in water while catalyticing anode aoxidize in water is electrolysed as hypochlorous acid, and hypochlorous acid is to giving up Ammonia nitrogen in water is aoxidized, qualified discharge after waste water is aoxidized 120 minutes in catalytic and oxidative electrolysis technology reactor 8.
Ozone used catalyst is with TiO2-Al2O3Composite is carrier, by containing Mn2+、Cu2+、Fe3+、Ce3+、Co2+ Concentration ratio is 1:1: 1:1:0.5 mixed liquor, is stirred at room temperature after dipping 4h, filtration washing, obtained catalyst is existed 2h is dried at 120 DEG C, is then calcined and is prepared from 300 DEG C.
The multigroup positive and negative pole of parallel arranged in catalytic and oxidative electrolysis technology reactor 8, positive and negative pole is alternately arranged；Anode is self-control titanium Base coated electrode, coating material is the PbO of Eu, Nd, Pt codope2；Negative electricity extremely graphite electrode；
Current density is 10mA/cm between pole plate, and pole plate spacing is 2cm；Oxidization time is 50 minutes.
Water outlet COD is determined as 48mg/L using national standard GB/T 11914-1989 dichromate titrations, and ammonia nitrogen uses HJ535- It is 0.5mg/L that 2009 Berthelot spectrophotometries, which determine content, and total nitrogen clears up purple using GB11894-89 alkaline chitinases Outer spectrophotometry content is 12mg/L, and processing cost is 39.8 yuan/m3。
Embodiment 2
The percolate that certain destructor plant rubbish is produced：COD is 4500mg/L, and ammonia nitrogen 1200mg/L, nitrate is 110mg/L, Total nitrogen is 1500mg/L.
The processing method provided using the present invention is handled：Pending percolate initially enters anoxic biological tank 1, keeps Sludge concentration is 5000mg/L in anoxic biological tank 1, and dissolved oxygen is in 0.3mg/L, and pH value is 7, and muddy water hybrid mode is used under liquid Mechanical agitation, hydraulic detention time is 25 hours, and the water outlet of anoxic biological tank 1 enters aerobic biofilter 2；
It is 3000mg/L to keep suspended sludge concentration in aerobic biofilter 2, and dissolved oxygen is in 4.0mg/L, and pH value is 8, and waterpower is stopped It is 25 hours to stay the time, and partial organic substances and ammonia nitrogen are decomposed into CO by the aerobic microbiological for being attached to carrier in water2、H2O、NO3 2-, The water part of aerobic biofilter 2 is back to anoxic biological tank 1 by reflux ratio 300% and removes NO3 2-, the water outlet of aerobic biofilter 2 Mud-water separation is carried out into biochemical sedimentation basin 3, base sludge is back to anoxic biological tank 1, and supernatant is adjusted pH by acid adding Section carries out Primary Oxidation to entering in iron-carbon micro-electrolysis pond 4 after 2.0；
Iron-carbon micro-electrolysis pond 4 carries out oxidation reaction 60 minutes, acid adding control water outlet pH 4.0, iron-carbon micro-electrolysis oxygen in course of reaction The hydrogen peroxide for changing water outlet addition 5 ‰ after removal partial organic substances enters the progress of Fenton oxidation pond 5 secondary oxidation；
Oxidization time of the waste water in Fenton oxidation pond 5 is 30 minutes, and it is laggard that Fenton oxidation water outlet adds alkali lye readjustment pH to 9.0 Enter ferric ion formation iron hydroxide flco precipitation in flocculation sedimentation tank 6, waste water, the bottom of sediment autoflocculation sedimentation basin 6 row Go out, supernatant enters catalytic ozonation reactor 7；
In catalytic ozonation reactor 7, waste water and the 100mg/L bottom of ozone autoreactor 7 enter, and urge in the reactor Three oxidations are carried out under the catalytic action of agent, oxidation enters catalytic and oxidative electrolysis technology unit 8 after 60 minutes, in applying direct current Effect is lower to carry out four oxidations, pole plate spacing 3cm, current density 10mA/cm, useless Organic substance in water catalyticing anode aoxidize it is same Shi Shuizhong chlorion is electrolysed as hypochlorous acid, and hypochlorous acid is aoxidized to the ammonia nitrogen in waste water, and waste water is in catalytic and oxidative electrolysis technology Qualified discharge after being aoxidized 60 minutes in unit 8.
Ozone used catalyst is with TiO2-Al2O3Composite is carrier, by containing Mn2+、Cu2+、Fe3+、Ce3+、Co2+ Concentration ratio is 0.8:0.8: 0.8:0.8:0.3 mixed liquor, is stirred at room temperature after dipping 4h, filtration washing, by urging for obtaining Agent dries 2h at 120 DEG C, is then calcined and is prepared from 300 DEG C.
The multigroup positive and negative pole of parallel arranged in catalytic and oxidative electrolysis technology reactor 8, positive and negative pole is alternately arranged；Anode is self-control titanium Base coated electrode, coating material is the IrO of Eu, Nd, Pt codope2；Negative electricity extremely graphite electrode；
Current density is 8mA/cm between pole plate, and pole plate spacing is 5cm；Oxidization time is 80 minutes.
Water outlet COD uses national standard GB/T 11914-1989 dichromate titrations for 35mg/L, and ammonia nitrogen uses HJ535-2009 It is 0.2mg/L that Berthelot spectrophotometry, which determines content, and total nitrogen clears up ultraviolet point using GB11894-89 alkaline chitinases It is 10mg/L that light photometry, which determines content, and processing cost is 17 yuan/m3。
Embodiment 3
The percolate that certain refuse landfill is produced：COD is 3000mg/L, and ammonia nitrogen 630mg/L, nitrate is 58mg/L, and total nitrogen is 740mg/L。
The processing method provided using the present invention is handled：Pending percolate initially enters anoxic biological tank 1, keeps Sludge concentration is 3000mg/L in anoxic biological tank, and dissolved oxygen is in 0.4mg/L, and pH value is 9, and muddy water hybrid mode uses machine under liquid Tool is stirred, and hydraulic detention time is 10 hours, and the water outlet of anoxic biological tank 1 enters aerobic filter tank 2；
It is 1000mg/L to keep suspended sludge concentration in aerobic filter tank 2, and dissolved oxygen is in 2.0mg/L, and pH value is 8, during hydraulic retention Between be 10 hours, partial organic substances and ammonia nitrogen are decomposed into CO by the aerobic microbiological for being attached to carrier in water2、H2O、NO3 2-, it is aerobic The water part of biofilter 2 is back to anoxic biological tank 1 by reflux ratio 100% and removes NO3 2-, the water outlet of aerobic biofilter 2 entrance Carry out mud-water separation in biochemical sedimentation basin 3, base sludge is back to anoxic biological tank 1, supernatant by acid adding by pH adjust to Enter after 3.0 in iron-carbon micro-electrolysis 4 and carry out Primary Oxidation；
Iron-carbon micro-electrolysis pond 4 carries out oxidation reaction 15 minutes, acid adding control water outlet pH 4.0, iron-carbon micro-electrolysis oxygen in course of reaction The hydrogen peroxide for changing water outlet addition 0.5 ‰ after removal partial organic substances enters the progress of Fenton oxidation pond 5 secondary oxidation；
Oxidization time of the waste water in Fenton oxidation pond 5 is 15 minutes, and it is laggard that Fenton oxidation water outlet adds alkali lye readjustment pH to 8.0 Enter ferric ion formation iron hydroxide flco precipitation in flocculation sedimentation tank 6, waste water, the bottom of sediment autoflocculation sedimentation basin 6 row Go out, supernatant enters catalytic ozonation reactor 7；
In catalytic ozonation reactor 7, waste water and 25mg/L ozone enter from the bottom of catalytic ozonation reactor 7, Three oxidations are carried out under the catalytic action of catalyst in catalytic ozonation reactor 7, oxidation is urged after 30 minutes into electrolysis Oxidation device 8, carries out four oxidations, pole plate spacing 5cm, current density 5mA/cm give up in the presence of applying direct current Chlorion of Organic substance in water while catalyticing anode is aoxidized in water is electrolysed as hypochlorous acid, and hypochlorous acid is to the ammonia nitrogen in waste water Aoxidized, qualified discharge after waste water is aoxidized 30 minutes in catalytic and oxidative electrolysis technology reactor 8.
Ozone used catalyst is with TiO2-Al2O3Composite is carrier, by containing Mn2+、Cu2+、Fe3+、Ce3+、Co2+ Concentration ratio is 1.2: 1.2: 1.2: 1.2:0.6 mixed liquor, is stirred at room temperature after dipping 4h, filtration washing, will obtain Catalyst 2h is dried at 120 DEG C, be then calcined and be prepared from 300 DEG C.
Catalytic and oxidative electrolysis technology reactor 8 is parallel arranged at least one set in square structure, catalytic and oxidative electrolysis technology reactor 8 Positive and negative pole, positive and negative pole is alternately arranged, and anode is ti-based coating electrode, and coating material is the TaO of Eu, Nd, Pt codope2； Negative electricity extremely stainless steel electrode；
Current density is 10mA/cm between pole plate, and pole plate spacing is 2cm；
Oxidization time is 90 minutes.
Water outlet COD uses national standard GB/T 11914-1989 dichromate titrations for 31mg/L, and ammonia nitrogen uses HJ535-2009 It is 0.1mg/L that Berthelot spectrophotometry, which determines content, and total nitrogen clears up ultraviolet point using GB11894-89 alkaline chitinases It is 8mg/L that light photometry, which determines content, and processing cost is 10 yuan/m3。
Integrated wastewater discharge standard（GB 89788-1996）
Each index value of before processing such as following table in embodiment 1-3 sample：
Each index value such as following table after method processing of the embodiment 1-3 sample by the present invention：
From the data in above table can be seen that the method processing through the present invention after refuse leachate, it is its COD, ammonia nitrogen, total Nitrogen index is far smaller than the numerical value in discharge standard；And the cost of its processing is relatively low, per side's control within 40 yuan.

Claims (9)

1. landfill leachate treatment is to its in line method up to standard, including following steps：
Anaerobic bio-treated --- Aerobic biological process --- iron-carbon micro-electrolysis --- Fenton oxidation --- ozone catalytic oxygen Change --- catalytic and oxidative electrolysis technology.
2. a kind of landfill leachate treatment as claimed in claim 1 is to its in line method up to standard, including following steps：
（1）Anaerobe is handled：
Percolate hydraulic retention in anoxic biological tank；
Dissolved oxygen in anoxic biological tank is controlled in below 0.5mg/L, pH value is 6-9；
Muddy water mixing uses mechanical agitation in anoxic biological tank；
（2）Aerobic microbiological processing：
Semi-soft biologic packing material is hung in aerobic biofilter, the packing volume ratio of described biologic packing material is 30-70%；
Percolate hydraulic retention in aerobic filter tank；
Dissolved oxygen in aerobic filter tank is controlled in 2.0-6.0mg/L；
The return sludge ratio that anoxic biological tank is back in aerobic filter tank is 100-400%；
(3) iron-carbon micro-electrolysis
Water inlet uses inorganic acid for adjusting pH value, and it is 2.0-3.0 to control inlet flow-patterm, and water outlet pH is 3.0-4.0；
In the step, using solid packing, light electrolysis oxidization time is 15-120 minutes；
（4）Fenton oxidation：
The hydrogen peroxide that mass concentration is 30% is added, the volume that hydrogen peroxide is added is percolate volume for 0.5-10 ‰；
Oxidization time is 15-60 minutes；
Fenton water outlet pH adds alkali to pull back to pH8.0-9.0；
（5）Catalytic ozonation：
Ozone used catalyst is added in catalytic ozonation reactor；
Ozone dosage is 25-200mg/L；
The ozone oxidation time is 30-120 minutes；
（6）Catalytic and oxidative electrolysis technology
The catalysis oxidation in catalytic and oxidative electrolysis technology reactor；In catalytic and oxidative electrolysis technology reactor parallel arranged at least one set anode, The pole plate that negative electrode is alternately arranged；
Current density is 5.0-20mA/cm between pole plate, and pole plate spacing is 1-5cm；
Oxidization time is 30-120 minutes.
3. a kind of landfill leachate treatment as claimed in claim 2 is to its in line method up to standard, it is characterised in that
Step（3）In, the packing material size used is 3-10cm, in the filler, and the mass fraction of iron powder is 68-72%, carbon dust Mass fraction is 15-22%, and Cu, Mn, Ti, Pd mol ratio are（1-3）:（0.5-1.5）: (0.5-1.5): (0.2-0.8)； By above-mentioned raw material mixed-forming, formed through 1200-1500 DEG C of anoxybiotic high temperature sintering.
4. a kind of landfill leachate treatment as claimed in claim 2 is to its in line method up to standard, it is characterised in that
Step（3）In, the packing material size used is 3-10cm, in the filler, and the mass fraction of iron powder is 70%, the matter of carbon dust It is 20% to measure fraction, and Cu, Mn, Ti, Pd mol ratio are 2:1:1:0.5；By above-mentioned raw material mixed-forming, through 1200-1500 DEG C Anoxybiotic high temperature sintering is formed.
5. a kind of landfill leachate treatment as claimed in claim 2 is to its in line method up to standard, it is characterised in that
Step（5）In, ozone used catalyst is with TiO2-Al2O3Composite is carrier, by containing Mn2+、Cu2+、Fe3+、Ce3 +、Co2+Concentration ratio is (0.8-1.2):( 0.8-1.2): (0.8-1.2):( 0.8-1.2):The mixed liquor of (0.3-0.6), Stirring is impregnated after 4h, filtration washing at room temperature, and obtained catalyst is dried into 2h at 120 DEG C, and system is then calcined at 300 DEG C It is standby to form.
6. a kind of landfill leachate treatment as claimed in claim 2 is to its in line method up to standard, it is characterised in that
Step（5）In, ozone used catalyst is with TiO2-Al2O3Composite is carrier, by containing Mn2+、Cu2+、Fe3+、Ce3 +、Co2+Concentration ratio is 1:1:1:1:0.5 mixed liquor, is stirred at room temperature after dipping 4h, filtration washing, by obtained catalyst 2h is dried at 120 DEG C, is then calcined and is prepared from 300 DEG C.
7. a kind of landfill leachate treatment as claimed in claim 2 is to its in line method up to standard, it is characterised in that
Parallel arranged at least one set positive and negative pole in catalytic and oxidative electrolysis technology reactor, positive and negative pole is alternately arranged；Anode is self-control titanium Base coated electrode, coating material is the PbO of Eu, Nd, Pt codope2、TaO2、IrO2In one or more；Negative electricity is extremely stainless Steel electrode or graphite electrode；
Current density is 5.0-20mA/cm between pole plate, and pole plate spacing is 1-5cm；Oxidization time is 30-120 minutes.
8. a kind of landfill leachate treatment as claimed in claim 2 is to its in line method up to standard, it is characterised in that step （2）In, semi-soft biologic packing material is inner support hanging filler, and this filler is using cotton fiber as surfacing, and interior is basic using PVC Material is composed in series as support, and with cordage.
9. a kind of landfill leachate treatment as claimed in claim 1 is to its in line method up to standard, including following steps：
（1）Anaerobic bio-treated：
Hydraulic detention time of the percolate in anoxic biological tank is 10-50 hours；
Keep sludge concentration 3000-9000mg/L in anoxic pond；
Dissolved oxygen in anoxic pond is controlled in below 0.5mg/L, and pH value is 6-9；
Anoxic pond muddy water hybrid mode uses mechanical agitation under liquid；
（2）Semi-soft biologic packing material is hung in aerobic biofilter, described biologic packing material packing volume ratio is 30-70%；
Hydraulic detention time of the percolate in aerobic filter tank is 10-50 hours；
Suspended sludge concentration 2000-5000mg/L in aerobic filter tank；
Dissolved oxygen in aerobic filter tank is controlled in 2.0-6.0mg/L；
The return sludge ratio that anoxic biological tank is back in aerobic filter tank is 100-400%；
(3) iron-carbon micro-electrolysis
Water inlet carries out pH regulations using sulfuric acid or hydrochloric acid, and it is 2.0-3.0 to control inlet flow-patterm, and water outlet pH is 3.0-4.0；
In the step, using solid packing, packing material size is 3-10cm；In the filler, the mass fraction of iron powder is 68-72%, carbon The mass fraction of powder is 15-22%, and Cu, Mn, Ti, Pd mol ratio are（1-3）:（0.5-1.5）: (0.5-1.5): (0.2- 0.8)；By above-mentioned raw material mixed-forming, formed through 1200-1500 DEG C of anoxybiotic high temperature sintering；
Light electrolysis oxidization time is 15-120 minutes；
（4）Fenton oxidation：
The hydrogen peroxide that mass concentration is 30% is added, the volume that hydrogen peroxide is added is percolate volume for 0.5-10 ‰；
Oxidization time is 15-60 minutes；
Fenton water outlet pH adds alkali to pull back to 8.0-9.0；
（5）Catalytic ozonation：
Catalytic ozonation reactor is tower structure, wherein being filled with ozone used catalyst, ozone used catalyst is with TiO2- Al2O3Composite is carrier, by containing Mn2+、Cu2+、Fe3+、Ce3+、Co2+Concentration ratio is (0.8-1.2):( 0.8-1.2): (0.8-1.2):( 0.8-1.2):The mixed liquor of (0.3-0.6), is stirred at room temperature after dipping 4h, filtration washing, by what is obtained Catalyst dries 2h at 120 DEG C, is then calcined and is prepared from 300 DEG C；
Ozone dosage is 25-200mg/L；
The ozone oxidation time is 30-120 minutes；
（6）Catalytic and oxidative electrolysis technology
Catalytic and oxidative electrolysis technology reactor is at least one set of positive and negative pole of parallel arranged, positive and negative pole alternating in square structure, reactor Arrangement, anode is ti-based coating electrode, and coating material is PbO2,IrO2,TaO2At least one of；Negative electricity extremely stainless steel electricity Pole or graphite electrode；
Current density is 5.0-20mA/cm between pole plate, and pole plate spacing is 1-5cm；
Oxidization time is 30-120 minutes.
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CN107902745A (en) * 2017-11-30 2018-04-13 浙江奇彩环境科技股份有限公司 A kind of processing method of landfill leachate thick water
CN108658372A (en) * 2018-05-17 2018-10-16 北京建筑大学 Anammox couples the method that electro-oxidation processes processing landfill leachate realizes depth carbon and nitrogen removal
CN108996821A (en) * 2018-07-26 2018-12-14 广东中微环保生物科技有限公司 A kind of processing system and processing method of landfill leachate
CN114751595A (en) * 2022-04-27 2022-07-15 广州市环境保护工程设计院有限公司 Landfill leachate treatment system and treatment method
CN115254870A (en) * 2022-06-16 2022-11-01 深圳市欧格尼绿氢科技有限公司 Method and system for treating garbage and/or leachate thereof through electrochemical degradation by two-step oxidation method to produce hydrogen jointly

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CN108658372A (en) * 2018-05-17 2018-10-16 北京建筑大学 Anammox couples the method that electro-oxidation processes processing landfill leachate realizes depth carbon and nitrogen removal
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CN115254870A (en) * 2022-06-16 2022-11-01 深圳市欧格尼绿氢科技有限公司 Method and system for treating garbage and/or leachate thereof through electrochemical degradation by two-step oxidation method to produce hydrogen jointly
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