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CN105502814A - Ozone catalytic oxidation combined biofilter deep processing coking wastewater process and device - Google Patents

Ozone catalytic oxidation combined biofilter deep processing coking wastewater process and device Download PDF

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Publication number
CN105502814A
CN105502814A CN201510906476.6A CN201510906476A CN105502814A CN 105502814 A CN105502814 A CN 105502814A CN 201510906476 A CN201510906476 A CN 201510906476A CN 105502814 A CN105502814 A CN 105502814A
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China
Prior art keywords
water
catalytic oxidation
oxidation tower
catalytic
filter
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CN201510906476.6A
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Inventor
盛军波
张垒
余刚强
肖建军
胡均智
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Wuhan Iron and Steel Co Ltd
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Wuhan Iron and Steel Group Corp
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Priority to CN201510906476.6A priority Critical patent/CN105502814A/en
Publication of CN105502814A publication Critical patent/CN105502814A/en
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/001Processes for the treatment of water whereby the filtration technique is of importance
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/722Oxidation by peroxides
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/725Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/78Treatment of water, waste water, or sewage by oxidation with ozone
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage

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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)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

The invention discloses an ozone catalytic oxidation combined biofilter deep processing coking wastewater process, comprising the following steps: (1) conveying coking wastewater from a coagulative precipitation tank to a multi-medium filter for filtering; (2) conveying filtered wastewater to an ozone catalytic ozonation reaction device for catalytic oxidation; (3) conveying oxidated wastewater to an intermediate water tank; (4) conveying the wastewater to a biofilter for filtering through a pump; (5) using the wastewater from the biofilter for different purposes. The invention further provides a catalytic ozonation combined biofilter deep processing coking wastewater device, which is reasonable in design, low in operation cost and capable of solving the difficult problem of deep processing and reuse of the coking wastewater and has very high engineering application value. The process solves the potential risk of unsafe factors and health harming of the coking wastewater to operators in a high pollution environment; operation is simple, operation cost is low and effluent quality meets different water using demands.

Description

Catalytic ozonation combination biological filter advanced treatment on coking wastewater technique and device
Technical field
The present invention relates to environmental technology field, specifically refer to a kind of catalytic ozonation combination biological filter advanced treatment on coking wastewater technique and device.
Background technology
Coking chemical waste water is the high concentrated organic wastewater produced in coal coke, gas purification and coking recovery of chemical products process, this wastewater biodegradability is poor, except the inorganic pollution beyond the region of objective existence such as ammonia, cyanogen and thiocyanate, sulfonium ion, chlorion, also containing organic pollutants such as heterocycle and polycyclc aromatic compound (PAHS), fatty compounds such as phenols, naphthalene, pyridine, quinoline, wastewater toxicity is large, and part studiedly turns out to be carcinogenic substance, ammonia nitrogen in high density, sulfide, prussiate have very strong restraining effect to microorganism active in addition, and Nitrogen removal effect is not good.At present, the main technique that coking chemical waste water generally adopts multi-form A/O biological denitrification process to process as it, rear auxiliary coagulating sedimentation etc., but in the rear water outlet of process, COD index is difficult to reach standard-required.Part iron enterprise has carried out coking wastewater deep treatment and reuse, reuse approach comprises wet quenching, blast furnace slag flushing, coal yard dust suppression and is directly used in industrial circulating water etc., but all there is operating environment difference in these methods, the problems such as secondary pollution produces or transfer, equipment, corrosive pipeline be serious.
" coking chemistry emission of industrial pollutants standard " (GB16171-2012) specifies, except waste water discharge pollutant concentration reaches except limit value, the burnt water displacement of unit ton can not more than 0.4m 3.Therefore carrying out advanced treatment and reuse to coking chemical waste water is reduce wastewater disposition, reduces the optimal selection of new water consumption.The present invention proposes to utilize more medium filter, catalytic ozonation, biological filter and reverse osmosis desalination new technology of combined and device, avoid the way causing secondary pollution by introducing other chemical agents etc., simultaneously, achieve and reduce Treatment of Coking Effluent cost, save a large amount of water of productive use, for the advanced treatment of coking chemical waste water and reuse provide economic, practical, an efficient advanced treatment process and apparatus system.
The outstanding problem that current coking wastewater deep treatment and reuse technology exist mainly contains: 1, by chemical agent advanced treatment of waste water (as adopted the strong oxidizers such as Fenton reagent, hypochlorite, ferrate), the method may introduce secondary pollution, there is the problem such as pipe network and equipment corrosion, increase follow-up desalination expense, to there is medicament add-on large for this technique simultaneously, the problems such as water quality is subject to flocculation impact effect outstanding, water quality is not easy to control; 2, coking chemical waste water is used for wet quenching or blast furnace slag flushing, Pollutants in Wastewater there occurs transfer, and by liquid phase to gas phase, operating environment is poor; 3, the dense water whereabouts after embrane method advanced treatment is also need the problem of solution badly.
Summary of the invention
Object of the present invention will provide a kind of reasonable in design exactly, running cost is cheap and have the catalytic ozonation combination biological filter advanced treatment on coking wastewater technique and device that very strong engineer applied is worth, and effectively can solve the difficult problem in coking wastewater deep treatment and reuse.
For achieving the above object, the invention provides a kind of catalytic ozonation combination biological filter advanced treatment on coking wastewater technique, it comprises the steps:
1) carrying out filtration treatment by being transported in more medium filter from mixed heavy pond coking chemical waste water out, to remove the suspended substance in waste water, obtaining filtering rear waste water;
2) waste water after filtration is delivered in catalytic ozonation reaction unit, through catalytic oxidation and the outer adding medicine H of ozone oxidation, catalyzer 2o 2synergistic oxidation effect, oxidation operation in waste water is become small organic molecule or inorganics, obtain be oxidized after waste water; Meanwhile, the residual ozone of effusion is transported to ozone destruct device;
3) waste water after oxidation is delivered to intermediate pool;
4) again by waste water by filtering in pump delivery to biological filter, to reduce SS, COD and the BOD in waste water, and denitrogenation dephosphorizing;
5) a biological filter waste water part is out used as defoamer use water, coal yard dust suppression or reclaimed water in biological process; A part of waste water carries out desalination by follow-up cartridge filter, reverse osmosis unit in addition, waste water recycling after desalination makes technique recirculated cooling water, and reverse osmosis unit reverse osmosis dense water is out used as blast-furnace slag cooling flushing cinder water, coal yard dust suppression or road-cleaning water.
Catalytic ozonation combination biological filter advanced treatment on coking wastewater technique, its key step: enter more medium filter by the suspended substance filtrate removal waste water from mixed heavy pond coking chemical waste water out, be beneficial to simultaneously and improve postorder catalytic ozonation efficiency, waste water in catalytic ozonation reaction unit through the catalytic oxidation of ozone oxidation, catalyzer and outer adding medicine H 2o 2synergistic oxidation effect, produce the extremely strong hydroxyl radical free radical of a large amount of oxidisability (OH), oxidation operation in waste water become small organic molecule or inorganics as CO 2, H 2o, wastewater biochemical improves, and meanwhile, the residual ozone of effusion enters ozone destruct device.Waste water enters intermediate pool after catalytic ozonation reaction, by pump delivery to biological filter, by having the effect of filtration in the process such as microbial flocculation and degraded that grows in filtrate concurrently, reduce the objectionable impuritiess such as SS, COD, the BOD in waste water, and can denitrogenation dephosphorizing, thus decrease oxidizing process and there is better effect.A biological filter waste water part out directly can be used as inferior grade water, defoamer use water, coal yard dust suppression, reclaimed water etc. in such as biological process; A part of waste water carries out desalination by follow-up cartridge filter, reverse osmosis system in addition, waste water recycling after process makes technique recirculated cooling water, and reverse osmosis dense water out can be directly used in other purposes such as blast-furnace slag cooling flushing cinder water, coal yard dust suppression, road-cleaning water.
The present invention also provides a kind of catalytic ozonation to combine biological filter advanced treatment on coking wastewater device, comprise be connected with valve by pipeline more medium filter, ozonizer, catalytic ozonation reaction unit, ozone destruct device, catalyzer chemicals dosing plant, biological filter, cartridge filter and reverse osmosis unit, it is characterized in that: the water outlet of described more medium filter is connected with the water-in of catalytic ozonation reaction unit with the pipeline of under meter by being provided with pump
Be connected with ozonizer by the pipeline being provided with gas blower bottom described catalytic ozonation reaction unit, catalytic ozonation reaction unit top is connected with ozone destruct device by pipeline, catalytic ozonation reaction unit top is also connected with the grug feeding jar of agitator by dosing pump, the water outlet of catalytic ozonation reaction unit is connected with the water-in of intermediate pool by pipeline, the biological filter water-in that the water outlet of intermediate pool is provided with aeration board by pipeline and inside is connected, the top of described biological filter is provided with backwashing water water outlet, the bottom of biological filter is connected with air-blaster by pipeline,
The water outlet of described biological filter is connected with cartridge filter water-in with the Backwash pipeline of dosing mouth by being provided with backwashing pump, described cartridge filter is provided with backwashing water discharge outlet, the water outlet of cartridge filter is connected with reverse osmosis unit water-in, and described reverse osmosis unit water outlet is connected to rising pipe and concentrated water drainage goes out pipe.
Further, described catalytic ozonation reaction unit is made up of pre-catalytic oxidation tower and catalytic oxidation tower tandem, the tower body of pre-catalytic oxidation tower and catalytic oxidation tower is vertical tubular structure, and the water outlet of pre-catalytic oxidation tower is connected with the water-in of catalytic oxidation tower by the pipeline being provided with pump;
Described pre-catalytic oxidation top of tower and catalytic oxidation top of tower are equipped with tail gas drain, and pre-catalytic oxidation top of tower is also provided with dosing mouth; Pre-catalytic oxidation tower inside and catalytic oxidation tower inside are equipped with water distribution board; Pre-catalytic oxidation tower inside is provided with dumped packing, and catalytic oxidation tower inside is provided with catalyst filling; Described pre-catalytic oxidation tower bottom and catalytic oxidation tower bottom are equipped with filler supporting plate, titanium matter aeration board and ozone inlet;
Described pre-catalytic oxidation tower is all connected with the gas inlet of ozone destruct device by pipeline with the tail gas drain of catalytic oxidation top of tower; Pre-catalytic oxidation tower is all connected with ozonizer by pipeline with the ozone inlet of catalytic oxidation tower.
Closer, described more medium filter is vertical cylinder shape multi-medium filtering device, comprises the filter body, supporting pipelines and the valve that are made up of cylindrical shell, cloth water assembly, supporting component; Described filter body inside is provided with backwash tracheae and filtrate, and filter body outside is provided with vent valve; Described filtrate is made up of Φ 0.5 ~ 2mm hard coal, Φ 3 ~ 6mm haydite and Φ 4 ~ 10mm quartz sand.
Closer, described dumped packing is any one in Raschig ring filler, Pall ring filler or Berl saddle, and filler dosage is 40% ~ 60% of pre-catalytic oxidation tower cylindrical shell;
Closer, described catalyst filling is that specific surface area is greater than 200m 2/ m 3and the burned diatomite of supported copper, iron, manganese or nickel, haydite or gac; Filler dosage is 45% ~ 60% of catalytic oxidation tower cylindrical shell volume;
Closer, described ozone destruct device adopts gac to absorb or KI solution absorption residual ozone.
Closer, described pre-catalytic oxidation tower and catalytic oxidation tower bottom are equipped with liquidometer, and the water outlet of liquidometer least significant end and pre-catalytic oxidation tower and catalytic oxidation tower is in same level;
Closer, the source of the gas of described ozonizer adopts oxygen.
Catalytic ozonation combination biological filter of the present invention advanced treatment on coking wastewater device, primarily of formations such as more medium filter, ozonizer, ozone destruct device, catalytic oxidation tower, catalyzer chemicals dosing plant, biological filter, cartridge filter, reverse osmosis units, (1) more medium filter can reduce the content of suspended substance, improves ozone reaction groove water treatment effect simultaneously; (2) ozonizer generates ozone, source of the gas is pure oxygen; (3) ozone of spilling or non-complete reaction destroys by ozone destruct device, reduces the pollution of environment to external world; (4) catalytic oxidation groove be by ozone and coking chemical waste water in catalytic oxidation groove by the oxidation of the organic substance of bio-refractory in coking chemical waste water by hydroxyl radical free radical, larger molecular organics in waste water and arene compound are degraded into small molecules or CO 2, to improve wastewater biodegradability; (5) catalyzer chemicals dosing plant adds external medicament, helps ozone and coking chemical waste water rapid reaction in catalytic oxidation groove, organic subsystem in degrading waste water; (6) biological filter is mainly through having the effect of filtration concurrently in the process such as microbial flocculation and degraded that grows in filtrate, reduce the objectionable impuritiess such as SS, COD, the BOD in waste water, and can denitrogenation dephosphorizing, thus decrease oxidizing process and there is better effect; (7) biological filter partial suspended thing out mainly filters by cartridge filter further, meets the inflow requirement of reverse osmosis unit system; (8) reverse osmosis unit is mainly to the further desalination of waste water, meets the high-grade water requirement of part; (9) from biological filter, waste water out can be directly used in the requirement of inferior grade water, defoamer use water, coal yard dust suppression etc. in such as deepening process; (10) blast-furnace slag cooling, flushing cinder water, coal yard dust suppression etc. can be directly used in from reverse osmosis system dense water out.
Above-mentioned more medium filter is conventional vertical cylinder shape multi-medium filtering device, is formed: (1) filter body, comprise 1. simplified primarily of with lower part; 2. cloth water assembly; 3. supporting component; (5) supporting pipelines and valve.Wherein filter body has 4. backwash tracheae; 5. filtrate; 6. vent valve (external) etc.Filtrate can select hard coal (Φ 0.5 ~ 2mm), haydite (Φ 3 ~ 6mm) and quartz sand (Φ 4 ~ 10mm) etc.Object is the concentration of suspension reduced further in waste water, reduces the material such as suspended substance, colloid, improves ozone utilising efficiency simultaneously.
Above-mentioned catalytic ozonation reaction unit is set to tandem reaction unit, and one is pre-reaction tower, and it two is reaction tower, and tower body is vertical tubular structure.Its top of pre-reaction tower is provided with water distribution board, emergent drain, ozone destruct device and tail gas drain, and middle part loads dumped packing, and as Raschig ring filler, Pall ring filler, Berl saddle etc., filler dosage is 40% ~ 60% of cylindrical shell; Bottom is provided with back up pad, water outlet, titanium matter aeration board.Its top of reaction tower is provided with water distribution board, emergent drain, ozone destruct device and tail gas drain, and middle part is provided with catalyst filling layer, and bottom is provided with back up pad, water outlet, titanium matter aeration board.In reaction tower, packing specific area should be greater than 200m 2/ m 3and the burned diatomite of the compounds such as supported copper, iron, manganese, nickel, haydite or gac.In catalytic ozonation reaction unit, filler dosage is 45% ~ 60% of volume; Packing support plate arranges aperture, and aperture should be less than packing material size, supports filler on the one hand, ensures that current pass through on the other hand.Catalytic ozonation reaction unit bottom should arrange liquidometer, and liquidometer least significant end and water outlet are in same level, and catalytic ozonation reaction unit bottom water level is higher than water outlet, guarantees that ozone can not overflow from water outlet.Ozonizer source of the gas adopts oxygen.Ozone tail gas breaking plant adopts the breaking plants such as gac absorption, the absorption of KI solution.
The medicament added in above-mentioned catalyzer chemicals dosing plant is mainly H 2o 2, H 2o 2/ Fe 2+one or both in (mol ratio 1:3).
Above-mentioned intermediate pool can be set to rectangular pool or tower-like tank, mainly plays stabilizing water quality, water yield effect.
Above-mentioned BAF adopts upflow type aerating biological filter, and bottom is furnished with water inlet pipe, back flushing water inlet pipe and aeration tube; Filler is haydite, and raising/filter tank aspect ratio is 1:1.5 ~ 1:3; The cobble of to be diameter be in bottom 100 ~ 150mm.Haydite particle diameter is 1.5 ~ 6.0mm, and tap density is 0.80 ~ 0.95g/cm 3, specific surface area is 2.5 ~ 6.0m 2/ g, porosity is 50% ~ 60%.A water part after the process of biological filter directly can be used as inferior grade water, defoamer use water, coal yard dust suppression, reclaimed water etc. in such as biological process.Biological filter backwashing water adopts the waste water after cartridge filter process.
Above-mentioned cartridge filter operation scheme adopts backwash type, chimney filter material can pottery, glass sand, plastics etc. multiple.Pore size filter is 0.5 ~ 120 μm of scope.When moving to intake-outlet differential water pressures and reaching 0.1MPa, should more renew cartridge.Its objective is for the subtitle substance of filtering behind biological filter (as suspended substance; fine particle etc.) and microorganism; to guarantee that water filtration precision and protection postorder film filtering element be not by the damage of large particulate matter; extend the reverse osmosis unit life-span, meet the normal operation of reverse osmosis system.Be provided with chemical feeding points before cartridge filter, add clorox sterilant and sodium bisulfite reductive agent respectively, to reduce the content entering bacterium in reverse osmosis desalinization system, and neutralize excessive chlorine residue, prevent chlorine residue from entering reverse osmosis system.
Above-mentioned reverse osmosis unit adopts modularized equipment.Object is to the further advanced treatment desalination of waste water, removes part COD, produce water and can be back to the high-grade water such as industrial circulating cooling water, dense water is mainly brine waste, can arrange directly outward, also can be used as blast-furnace slag cooling, flushing cinder water, coal yard dust suppression etc.
The invention has the advantages that:
(1) the present invention is reasonable in design, and running cost is cheap, solves the difficult problem in coking wastewater deep treatment and reuse, has very strong engineer applied and is worth.
(2) the invention solves the potential risk to operator's unsafe factor and health risk under the high pollution environment of coking chemical waste water.
(3) the present invention is simple to operate, and running cost is low, and effluent quality can meet different water requirement.
Accompanying drawing explanation
Fig. 1 is integrated artistic schema of the present invention.
Fig. 2 is the structural representation of catalytic ozonation reaction unit of the present invention.
Fig. 3 is UV spectral scan figure before and after Treatment of Coking Effluent of the present invention.
In figure: 1, more medium filter, 2, backwashing water water outlet, 3, pump, 4, under meter, 5, pre-catalytic oxidation tower, 6, water distribution board, 7, dumped packing, 8, liquidometer, 9, filler supporting plate, 10, titanium matter aeration board, 11, ozonizer, 12, gas blower, 13, dosing pump, 14, grug feeding jar, 15, agitator, 16, catalytic oxidation tower, 17, catalyst filling, 18, ozone destruct device; 19, tail gas row mouth, 20, intermediate pool, 21, biological filter, 22, aeration board, 23, air-blaster, 24, backwashing water water outlet, 25, backwashing pump, 26, cartridge filter, 27, reverse osmosis unit.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
As shown in Figure 1, catalytic ozonation combination biological filter advanced treatment on coking wastewater device, comprise be connected with valve by pipeline more medium filter 1, ozonizer 11, catalytic ozonation reaction unit, ozone destruct device 18, catalyzer chemicals dosing plant, biological filter 21, cartridge filter 26 and reverse osmosis unit 27, the water outlet of more medium filter 1 is connected with the water-in of catalytic ozonation reaction unit with the pipeline of under meter 4 by being provided with pump 3
Pipeline by being provided with gas blower 12 bottom catalytic ozonation reaction unit is connected with ozonizer 11, catalytic ozonation reaction unit top is connected with ozone destruct device 18 by pipeline, catalytic ozonation reaction unit top is also connected with the grug feeding jar 14 of agitator 15 by dosing pump 13, the water outlet of catalytic ozonation reaction unit is connected by the water-in of pipeline with intermediate pool 20, biological filter 21 water-in that the water outlet of intermediate pool 20 is provided with aeration board 22 by pipeline and inside is connected, the top of biological filter 21 is provided with backwashing water water outlet 24, the bottom of biological filter 21 is connected with air-blaster 23 by pipeline,
The water outlet of biological filter 21 is connected with cartridge filter 26 water-in with the Backwash pipeline of dosing mouth by being provided with backwashing pump 25, cartridge filter 26 is provided with backwashing water discharge outlet, the water outlet of cartridge filter 26 is connected with reverse osmosis unit 27 water-in, and reverse osmosis unit 27 water outlet is connected to rising pipe and concentrated water drainage goes out pipe.
Catalytic ozonation reaction unit is made up of pre-catalytic oxidation tower 5 and catalytic oxidation tower 16 tandem, the tower body of pre-catalytic oxidation tower 5 and catalytic oxidation tower 16 is vertical tubular structure, and the water outlet of pre-catalytic oxidation tower 5 is connected with the water-in of catalytic oxidation tower 16 by the pipeline being provided with pump 3;
Pre-catalytic oxidation tower 5 top and catalytic oxidation tower 16 top are equipped with tail gas drain, and pre-catalytic oxidation tower 5 top is also provided with dosing mouth; Pre-catalytic oxidation tower 5 inside and catalytic oxidation tower 16 inside are equipped with water distribution board 6; Pre-catalytic oxidation tower 5 inside is provided with dumped packing 7, and catalytic oxidation tower 16 inside is provided with catalyst filling 17; Pre-catalytic oxidation tower 5 bottom and catalytic oxidation tower 16 bottom are equipped with filler supporting plate 9, titanium matter aeration board 10 and ozone inlet;
Pre-catalytic oxidation tower 5 is all connected by the gas inlet of pipeline with ozone destruct device 18 with the tail gas drain at catalytic oxidation tower 16 top; Pre-catalytic oxidation tower 5 is all connected with ozonizer 11 by pipeline with the ozone inlet of catalytic oxidation tower 16.
More medium filter 1 is vertical cylinder shape multi-medium filtering device, comprises the filter body, supporting pipelines and the valve that are made up of cylindrical shell, cloth water assembly, supporting component; Filter body inside is provided with backwash tracheae and filtrate, and filter body outside is provided with vent valve; Filtrate is made up of Φ 0.5 ~ 2mm hard coal, Φ 3 ~ 6mm haydite and Φ 4 ~ 10mm quartz sand.
Dumped packing 7 is any one in Raschig ring filler, Pall ring filler or Berl saddle, and filler dosage is 40% ~ 60% of pre-catalytic oxidation tower 5 cylindrical shell;
Catalyst filling 17 is greater than 200m for specific surface area 2/ m 3and the burned diatomite of supported copper, iron, manganese or nickel, haydite or gac; Filler dosage is 45% ~ 60% of catalytic oxidation tower 16 cylindrical shell volume; Ozone destruct device 18 adopts gac to absorb or KI solution absorbs residual ozone.
Pre-catalytic oxidation tower 5 and catalytic oxidation tower 16 bottom are equipped with liquidometer 8, and the water outlet of liquidometer 8 least significant end and pre-catalytic oxidation tower 5 and catalytic oxidation tower 16 is in same level; The source of the gas of ozonizer 11 adopts oxygen.
Catalytic ozonation combination biological filter of the present invention advanced treatment on coking wastewater technique, it comprises the steps:
1) carrying out filtration treatment by being transported in more medium filter 1 from mixed heavy pond coking chemical waste water out, to remove the suspended substance in waste water, obtaining filtering rear waste water;
2) waste water after filtration is delivered in catalytic ozonation reaction unit, through catalytic oxidation and the outer adding medicine H of ozone oxidation, catalyzer 2o 2synergistic oxidation effect, oxidation operation in waste water is become small organic molecule or inorganics, obtain be oxidized after waste water; Meanwhile, the residual ozone of effusion is transported to ozone destruct device 18;
3) waste water after oxidation is delivered to intermediate pool 20;
4) again by waste water by filtering in pump delivery to biological filter 21, to reduce SS, COD and the BOD in waste water, and denitrogenation dephosphorizing;
5) a biological filter 21 waste water part is out used as defoamer use water, coal yard dust suppression or reclaimed water in biological process; A part of waste water carries out desalination by follow-up cartridge filter 26, reverse osmosis unit 27 in addition, waste water recycling after desalination makes technique recirculated cooling water, and reverse osmosis unit 27 reverse osmosis dense water is out used as blast-furnace slag cooling flushing cinder water, coal yard dust suppression or road-cleaning water.
The present invention enters more medium filter 1 by suspended substance, the colloidal type material filtrate removal waste water from mixed heavy pond coking chemical waste water out, be beneficial to and improve postorder ozone catalytic efficiency, waste water will produce the extremely strong hydroxyl radical free radical (OH) of a large amount of oxidisability after under the catalytic ozonation of pre-catalytic oxidation tower 5, catalytic oxidation tower 16 and the synergy of outer adding medicine, oxidation operation in waste water is become small organic molecule or inorganics as CO 2, H 2o, wastewater biochemical improves, and meanwhile, the residual ozone of effusion enters ozone destruct device 18.Waste water is after intermediate pool 20 is stable, biological filter 21 will be inputted in waste water by pump, by having the effect of filtration in the process such as microbial flocculation and degraded that grows in filter concurrently, reduce the objectionable impuritiess such as SS, COD, the BOD in waste water, and can denitrogenation dephosphorizing, thus improve effluent quality further.Biological filter a part of water outlet out directly can be used as inferior grade water, defoamer use water, coal yard dust suppression, reclaimed water etc. in such as biological process; A part of waste water carries out desalination by follow-up cartridge filter 26, reverse osmosis system 27 in addition, waste water recycling after process makes technique recirculated cooling water, and reverse osmosis dense water out can be directly used in other purposes such as blast-furnace slag cooling flushing cinder water, coal yard dust suppression, road-cleaning water.
Catalytic ozonation reaction unit as shown in Figure 2.Water enters the pre-catalytic oxidation tower 5 of ozone and ozone countercurrent reaction by pump 3, and enter catalytic oxidation tower 16 and ozone countercurrent reaction again after reaction again, reacted waste water flows out from tower bottom.Ozone pre-catalytic oxidation tower 5 is vertical tubular structure, and its top is provided with water distribution board 6, packing layer 7, liquidometer 8 and filler supporting plate 9, titanium matter aeration board 10.Ozone row outside ozone destruct device 18 and tail gas drain 19 that unreacted is complete.Middle part loads dumped packing, and as Raschig ring filler, Pall ring filler, Berl saddle etc., filler dosage is 40% ~ 60% of cylindrical shell.Packing support plate 9 arranges aperture, and aperture should be less than packing material size, supports filler on the one hand, ensures that current pass through on the other hand.Ozone pre-catalytic oxidation tower 5 bottom should arrange liquidometer 8, and liquidometer 8 least significant end and water outlet are in same level, and ozone pre-catalytic oxidation tower 5 bottom water level is higher than water outlet, guarantees that ozone can not overflow from water outlet.Catalytic ozonation reaction tower packing support plate air vent aperture is 1 ~ 2mm, and the material of back up pad is titanium plate.
Catalytic ozonation reaction tower 16 fills catalyst filling 17, and its specific surface area is greater than 200m 2/ m 3, filler is the burned diatomite of the compounds such as supported copper, iron, manganese, nickel, haydite or gac.Loading catalyst filling 17 dosage in catalytic ozonation reaction tower 16 is 45% ~ 60% of volume.Titanium matter aeration board 10 adopts titanium matter aerator.Ozonizer 11 source of the gas adopts oxygen.Ozone tail gas breaking plant 18 adopts the rear emptying of the process such as gac absorption, the absorption of KI solution.Catalytic ozonation reaction tower 16 bottom construction is identical with pre-catalytic oxidation tower 5 structure, does not repeat them here.
As shown in Figure 3 be in the invention process process, the UV scanning curve before and after Treatment of Coking Effluent.Institute's adding medicine is H 2o 2, concentration is 6.5mmol/L.As can be seen from Fig. 3 curve, after this system depth process, waste water absorbancy significantly reduces, and illustrates that the most of organism in waste water is degraded or mineralising.
More medium filter 1 in the present embodiment, grug feeding jar 14, intermediate pool 20, biological filter 21, cartridge filter 26 and reverse osmosis unit system 27 with reference to Practical Project operation scheme, can illustrate at this no longer one by one.

Claims (9)

1. a catalytic ozonation combination biological filter advanced treatment on coking wastewater technique, it comprises the steps:
1) carrying out filtration treatment by being transported in more medium filter (1) from mixed heavy pond coking chemical waste water out, to remove the suspended substance in waste water, obtaining filtering rear waste water;
2) waste water after filtration is delivered in catalytic ozonation reaction unit, through catalytic oxidation and the outer adding medicine H of ozone oxidation, catalyzer 2o 2synergistic oxidation effect, oxidation operation in waste water is become small organic molecule or inorganics, obtain be oxidized after waste water; Meanwhile, the residual ozone of effusion is transported to ozone destruct device (18);
3) waste water after oxidation is delivered to intermediate pool (20);
4) again waste water is filtered to biological filter (21) are middle by pump delivery, to reduce SS, COD and the BOD in waste water, and denitrogenation dephosphorizing;
5) biological filter (21) waste water part is out used as defoamer use water, coal yard dust suppression or reclaimed water in biological process; A part of waste water carries out desalination by follow-up cartridge filter (26), reverse osmosis unit (27) in addition, waste water recycling after desalination makes technique recirculated cooling water, and reverse osmosis unit (27) reverse osmosis dense water is out used as blast-furnace slag cooling flushing cinder water, coal yard dust suppression or road-cleaning water.
2. a catalytic ozonation combination biological filter advanced treatment on coking wastewater device, comprise the more medium filter (1) be connected with valve by pipeline, ozonizer (11), catalytic ozonation reaction unit, ozone destruct device (18), catalyzer chemicals dosing plant, biological filter (21), cartridge filter (26) and reverse osmosis unit (27), it is characterized in that: the water outlet of described more medium filter (1) is connected with the water-in of catalytic ozonation reaction unit with the pipeline of under meter (4) by being provided with pump (3),
Pipeline by being provided with gas blower (12) bottom described catalytic ozonation reaction unit is connected with ozonizer (11), catalytic ozonation reaction unit top is connected with ozone destruct device (18) by pipeline, catalytic ozonation reaction unit top is also connected with the grug feeding jar (14) of agitator (15) by dosing pump (13), the water outlet of catalytic ozonation reaction unit is connected by the water-in of pipeline with intermediate pool (20), biological filter (21) water-in that the water outlet of intermediate pool (20) is provided with aeration board (22) by pipeline and inside is connected, the top of described biological filter (21) is provided with backwashing water water outlet (24), the bottom of biological filter (21) is connected with air-blaster (23) by pipeline,
The water outlet of described biological filter (21) is connected with cartridge filter (26) water-in with the Backwash pipeline of dosing mouth by being provided with backwashing pump (25), described cartridge filter (26) is provided with backwashing water discharge outlet, the water outlet of cartridge filter (26) is connected with reverse osmosis unit (27) water-in, and described reverse osmosis unit (27) water outlet is connected to rising pipe and concentrated water drainage goes out pipe.
3. catalytic ozonation combination biological filter according to claim 2 advanced treatment on coking wastewater device, it is characterized in that: described catalytic ozonation reaction unit is made up of pre-catalytic oxidation tower (5) and catalytic oxidation tower (16) tandem, the tower body of pre-catalytic oxidation tower (5) and catalytic oxidation tower (16) is vertical tubular structure, and the water outlet of pre-catalytic oxidation tower (5) is connected with the water-in of catalytic oxidation tower (16) by the pipeline being provided with pump (3);
Described pre-catalytic oxidation tower (5) top and catalytic oxidation tower (16) top are equipped with tail gas drain, and pre-catalytic oxidation tower (5) top is also provided with dosing mouth; Pre-catalytic oxidation tower (5) inside and catalytic oxidation tower (16) inside are equipped with water distribution board (6); Pre-catalytic oxidation tower (5) inside is provided with dumped packing (7), and catalytic oxidation tower (16) inside is provided with catalyst filling (17); Described pre-catalytic oxidation tower (5) bottom and catalytic oxidation tower (16) bottom are equipped with filler supporting plate (9), titanium matter aeration board (10) and ozone inlet;
Described pre-catalytic oxidation tower (5) is all connected by the gas inlet of pipeline with ozone destruct device (18) with the tail gas drain at catalytic oxidation tower (16) top; Pre-catalytic oxidation tower (5) is all connected with ozonizer (11) by pipeline with the ozone inlet of catalytic oxidation tower (16).
4. catalytic ozonation combination biological filter according to claim 3 advanced treatment on coking wastewater device, it is characterized in that: described more medium filter (1) is vertical cylinder shape multi-medium filtering device, comprises the filter body, supporting pipelines and the valve that are made up of cylindrical shell, cloth water assembly, supporting component; Described filter body inside is provided with backwash tracheae and filtrate, and filter body outside is provided with vent valve; Described filtrate is made up of Φ 0.5 ~ 2mm hard coal, Φ 3 ~ 6mm haydite and Φ 4 ~ 10mm quartz sand.
5. the catalytic ozonation combination biological filter advanced treatment on coking wastewater device according to claim 3 or 4, it is characterized in that: described dumped packing (7) is Raschig ring filler, in Pall ring filler or Berl saddle any one, filler dosage is 40% ~ 60% of pre-catalytic oxidation tower 5 cylindrical shell.
6. the catalytic ozonation combination biological filter advanced treatment on coking wastewater device according to claim 3 or 4, is characterized in that: described catalyst filling (17) is greater than 200m for specific surface area 2/ m 3and the burned diatomite of supported copper, iron, manganese or nickel, haydite or gac; Filler dosage is 45% ~ 60% of catalytic oxidation tower (16) cylindrical shell volume.
7. the catalytic ozonation combination biological filter advanced treatment on coking wastewater device according to claim 3 or 4, is characterized in that: described ozone destruct device (18) adopts gac to absorb or KI solution absorbs residual ozone.
8. the catalytic ozonation combination biological filter advanced treatment on coking wastewater device according to claim 3 or 4, it is characterized in that: described pre-catalytic oxidation tower (5) and catalytic oxidation tower (16) bottom are equipped with liquidometer (8), and the water outlet of liquidometer (8) least significant end and pre-catalytic oxidation tower (5) and catalytic oxidation tower (16) is in same level.
9. the catalytic ozonation combination biological filter advanced treatment on coking wastewater device according to claim 3 or 4, is characterized in that: the source of the gas of described ozonizer (11) adopts oxygen.
CN201510906476.6A 2015-12-09 2015-12-09 Ozone catalytic oxidation combined biofilter deep processing coking wastewater process and device Pending CN105502814A (en)

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Publication number Priority date Publication date Assignee Title
CN108117228A (en) * 2016-11-29 2018-06-05 中国石油天然气股份有限公司 Salt water treatment device
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CN109019959A (en) * 2018-08-09 2018-12-18 中国电子系统工程第二建设有限公司 A kind of processing unit of strong complex state heavy metal wastewater thereby and its discharge and reuse technology
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CN113830928A (en) * 2021-10-21 2021-12-24 江苏鑫林环保设备有限公司 High-efficient oxidation decoloration device
CN115745275A (en) * 2022-11-23 2023-03-07 中冶南方都市环保工程技术股份有限公司 Coking wastewater treatment method and system
CN117069302A (en) * 2023-08-16 2023-11-17 南京工大环境科技有限公司 High COD strong brine defluorination and hardness removal process, catalytic oxidation process and device
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