CN104876403A - Process and device for advanced treatment and reuse of coking wastewater - Google Patents
Process and device for advanced treatment and reuse of coking wastewater Download PDFInfo
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- CN104876403A CN104876403A CN201510317096.9A CN201510317096A CN104876403A CN 104876403 A CN104876403 A CN 104876403A CN 201510317096 A CN201510317096 A CN 201510317096A CN 104876403 A CN104876403 A CN 104876403A
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Abstract
The invention discloses a process for advanced treatment and reuse of coking wastewater. The process comprises the following steps of firstly, performing precipitation treatment in a mixed precipitation tank; secondly, performing filtering treatment in a multi-media filter; thirdly, performing a catalytic oxidation reaction in an ozone catalytic oxidation reactor; fourthly, conveying the wastewater subjected to the catalytic oxidation reaction to a middle water tank and then conveying the wastewater to a membrane bioreactor (MBR); fifthly, directly using the wastewater from the MBR as water for a defoaming agent in the biochemical process, dust control in a coal storage yard and domestic miscellaneous water; or sixthly, conveying the wastewater from the MBR to a security filter for further filtering treatment; seventhly, conveying the wastewater to a reverse osmosis device for removing salts. The invention also discloses a device for advanced treatment and reuse of the coking wastewater. The process and the device have the advantages of reasonable design, high engineering application value, simpleness in operation and low operation cost; water quality of effluent can meet different water consumption demands.
Description
Technical field
The present invention relates to environmental technology field, refer to it is a kind of coking wastewater deep treatment reuse technology and device particularly.
Background technology
Coking chemical waste water is a kind of trade effluent of generally acknowledged difficult for biological degradation, its difficulty is that the biodegradability of waste water is poor, except inorganic pollution beyond the region of objective existences such as ammonia, cyanogen and thiocyanates, also be difficult to biological degradation containing the heterocycles such as phenols, naphthalene, pyridine, quinoline and polycyclc aromatic compound (PAHS), these materials can produce long-range effects to environment, 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, 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.
On January 1st, 2015 rises, newly-built enterprise pollution discharge standard (GB16171-2012) during existing coal chemical enterprise will perform " coking chemistry emission of industrial pollutants standard ".Therefore carrying out advanced treatment and reuse to coking chemical waste water is reduce wastewater disposition, reduces the optimal selection of new water consumption, and seeks a kind of advanced treatment of efficient, low cost and reuse technology is the active demand of current coking wastewater deep treatment process.The object of the invention is to change conventional depth treatment process, propose and utilize catalytic ozonation, biological filter and immersion MBR membrane bioreactor new technology of combined and device, avoid the way causing secondary pollution by introducing other chemical agents etc., simultaneously, also 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 device.
The outstanding problem that current coking wastewater deep treatment and reuse technology exist has following content: 1, by chemical agent advanced treatment of waste water (as adopted Fenton reagent etc.), the method may introduce secondary pollution, there is the problem such as pipe network and equipment corrosion, increase follow-up desalination expense; 2, coking chemical waste water is used for wet quenching or blast furnace slag flushing, Pollutants in Wastewater there occurs transfer, and operating environment is poor; 3, the dense water whereabouts after embrane method desalination advanced treatment is also need the problem of solution badly.
Summary of the invention
Object of the present invention will provide a kind of coking wastewater deep treatment reuse technology and device exactly.
For achieving the above object, the invention provides a kind of coking wastewater deep treatment reuse technology, it is characterized in that: it comprises the steps:
(1) waste water is delivered in mixed heavy pond and carry out precipitation process, the coking chemical waste water after being precipitated;
(2) be delivered to more medium filter from mixed heavy pond coking chemical waste water out and carry out filtration treatment, to reduce the content of the suspended substance in waste water further;
(3) coking chemical waste water after filtration is delivered to the catalytic oxidation carrying out ozone oxidation, catalyzer in catalytic ozonation reactor, make the oxidation of organic substance by hydroxyl radical free radical of bio-refractory in coking chemical waste water, larger molecular organics in waste water and arene compound are degraded into small molecules or CO
2and water; Meanwhile, the residual ozone of effusion enters ozone destruct device;
(4) waste water after oxidation is delivered in middle tank, MBR membrane bioreactor is delivered to after being reduced by ozone concn in waste water further by the effect of aerating apparatus, ozone-decomposing agent in middle tank, by biological degradation, the crown_interception of high-concentration activated sludge, to the further biochemical degradation of micromolecular compound, also retain partial suspended thing simultaneously;
(5) waste water out from MBR membrane bioreactor is directly used as defoamer use water, coal yard dust suppression and reclaimed water in biological process; Or:
(6) waste water out from MBR membrane bioreactor is delivered to further filtration treatment in cartridge filter, filtering is partial suspended thing wherein;
(7) waste water after security personnel filter is delivered in reverse osmosis unit and carries out further desalination, gained desalination waste water recycling makes technique recirculated cooling water, and reverse osmosis dense water is out as blast-furnace slag cooling flushing cinder water, coal yard dust suppression water, road-cleaning water.
As a kind of preferred version, in described step (3), in catalytic ozonation reactor, filler is burned diatomite, haydite or gac, and packing specific area is greater than 200m
2/ m
3; In catalytic ozonation reactor, filler dosage is 25 ~ 60% of catalytic ozonation reactor volume; Ozonizer source of the gas adopts air or oxygen.
As another preferred version, in described step (4), middle tank arranges aerating apparatus and ozone-decomposing agent; Aerating apparatus adopts titanium matter aeration board, and source of the gas adopts air; Smelly decomposition agent adopts the oxide compound of Mn, Cu as active ingredient, and carrier adopts γ-Al
2o
3, TiO
2, SiO
2, several mixture of molecular sieve, gac or more; Ozone-decomposing agent filler dosage is 15 ~ 35% of middle tank volume.
As another preferred version, in described step (6), the chimney filter material of cartridge filter is pottery, glass sand or plastics; Pore size filter is 0.5 ~ 120 μm; Be provided with chemical feeding points before described cartridge filter, add clorox sterilant and sodium bisulfite respectively as reductive agent.
Present invention also offers a kind of device utilizing above-mentioned coking wastewater deep treatment reuse technology, this system comprises more medium filter, catalytic ozonation reactor, ozonizer, ozone destruct device, middle tank, MBR membrane bioreactor, cartridge filter, reverse osmosis unit, it is characterized in that: the import of described more medium filter 1 is connected with water inlet pipe and back flushing water inlet pipe respectively, the outlet of more medium filter is connected with the import of catalytic ozonation reactor and back flushing rising pipe respectively, the outlet of catalytic ozonation reactor is connected with the import of middle tank, the ozone input aperture of catalytic ozonation reactor is connected with ozonizer by ozone transport conduit, the ozone delivery port of catalytic ozonation reactor is connected with the import of ozone destruct device by pipeline, the outlet of ozone destruct device is connected with the exhaust pipe being provided with tail gas drain, the outlet of middle tank is connected with the import of MBR membrane bioreactor, and the outlet of MBR membrane bioreactor is connected with the import of cartridge filter, and the outlet of cartridge filter is connected with the import of reverse osmosis unit, the outlet of reverse osmosis unit is connected with dense water pipe and technological cycle water-cooled tube respectively, described cartridge filter top is provided with tensimeter, is provided with outer row's mouth bottom cartridge filter,
Also comprise air-blaster, described air-blaster is connected with the bottom of middle tank by the first pneumatic tube being provided with air flowmeter, air-blaster is connected with the bottom of MBR membrane bioreactor by the second pneumatic tube being provided with variable valve, and described middle tank is all connected with sludge treatment pipeline by sludge pump with the mud delivery port of MBR membrane bioreactor.
Further, the filtrate in described more medium filter is the quartz sand of the hard coal of particle diameter Φ 0.5 ~ 2mm, the haydite of particle diameter Φ 3 ~ 6mm or particle diameter Φ 4 ~ 10mm.
Further, described catalytic ozonation reactor is vertical tubular structure, tubular structure inside is provided with water distribution board, catalyst filling layer, filler supporting plate and titanium matter aeration board from top to bottom successively, and the top of tubular structure is provided with emergent drain, and the outer wall of tubular structure is provided with liquidometer.
Further, described middle tank inside is provided with the netted baffle plate in top from top to bottom successively, ozone-decomposing agent lower support plate and aerating apparatus; Described aerating apparatus is titanium matter aeration board.
Further, described MBR membrane bioreactor adopts immersion MBR membrane bioreactor, and aeration form adopts continuous aeration, and source of the gas adopts air.
Further, the entrance end of described cartridge filter is provided with chemical feeding points, and the chimney filter material in cartridge filter is any one in pottery, glass sand or plastics; The pore size filter scope of cartridge filter is 0.5 ~ 120 μm.
The invention has the advantages that:
One, this technique and apparatus design rationally, solve the difficult problem in coking wastewater deep treatment and reuse, have very strong engineer applied and are worth;
Its two, this technique and device solve the potential risk to operator's unsafe factor and health risk under the high pollution environment of coking chemical waste water;
Its three, this technique and device simple to operate, running cost is low, and effluent quality can meet different water requirement.
Accompanying drawing explanation
Fig. 1 is processing technological flow schematic diagram of the present invention.
Fig. 2 is catalytic ozonation reactor schematic diagram of the present invention.
Fig. 3 is middle tank schematic diagram of the present invention.
Fig. 4 be the embodiment of the present invention Treatment of Coking Effluent before and after UV spectral scan figure.
In Fig. 1: 1, more medium filter; 2, backwashing water outlet; 3, pump; 4, under meter; 5, catalytic ozonation reactor; 6, water-distributing device; 7, ozone catalyst packing layer; 8, liquidometer; 9, filler supporting plate; 10, aeration board; 11, gas meter; 12, gas blower; 13, ozonizer; 14, ozone destruct device; 15, tail gas drain; 16, middle tank; 17, baffle plate; 18, ozone-decomposing agent filler; 19, packing support plate; 20, aerator; 21, air flowmeter; 22, air-blaster; 23, variable valve; 24, MBR membrane bioreactor; 25, air aeration device; 26, sludge pump; 27, cartridge filter; 28, tensimeter; 29, outer row's mouth; 30, reverse osmosis unit.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Coking wastewater deep treatment reuse technology provided by the present invention, concrete steps are as follows:
(1) waste water is delivered in mixed heavy pond and carry out precipitation process, the coking chemical waste water after being precipitated;
(2) be delivered to more medium filter from mixed heavy pond coking chemical waste water out and carry out filtration treatment, to reduce the content of the suspended substance in waste water further;
(3) coking chemical waste water after filtration is delivered to the catalytic oxidation carrying out ozone oxidation, catalyzer in catalytic ozonation reactor, make the oxidation of organic substance by hydroxyl radical free radical of bio-refractory in coking chemical waste water, larger molecular organics in waste water and arene compound are degraded into small molecules or CO
2and water; Meanwhile, the residual ozone of effusion enters ozone destruct device;
(4) waste water after oxidation is delivered in middle tank, MBR membrane bioreactor is delivered to after being reduced by ozone concn in waste water further by the effect of aerating apparatus, ozone-decomposing agent in middle tank, by biological degradation, the crown_interception of high-concentration activated sludge, to the further biochemical degradation of micromolecular compound, also retain partial suspended thing simultaneously;
(5) waste water out from MBR membrane bioreactor is directly used as defoamer use water, coal yard dust suppression and reclaimed water in biological process; Or:
(6) waste water out from MBR membrane bioreactor is delivered to further filtration treatment in cartridge filter, filtering is partial suspended thing wherein;
(7) waste water after security personnel filter is delivered in reverse osmosis unit and carries out further desalination, gained desalination waste water recycling makes technique recirculated cooling water, and reverse osmosis dense water is out as blast-furnace slag cooling flushing cinder water, coal yard dust suppression water, road-cleaning water.
In step (3), in catalytic ozonation reactor, filler is burned diatomite, haydite or gac, and packing specific area is greater than 200m
2/ m
3; In catalytic ozonation reactor, filler dosage is 25 ~ 60% of catalytic ozonation reactor volume; Ozonizer source of the gas adopts air or oxygen.
In step (4), middle tank arranges aerating apparatus and ozone-decomposing agent; Aerating apparatus adopts titanium matter aeration board, and source of the gas adopts air; Smelly decomposition agent adopts the oxide compound of Mn, Cu as active ingredient, and carrier adopts γ-Al
2o
3, TiO
2, SiO
2, several mixture of molecular sieve, gac or more; Ozone-decomposing agent filler dosage is 15 ~ 35% of middle tank volume.
In step (6), the chimney filter material of cartridge filter is pottery, glass sand or plastics; Pore size filter is 0.5 ~ 120 μm; Be provided with chemical feeding points before cartridge filter, add clorox sterilant and sodium bisulfite respectively as reductive agent.
As shown in Figure 1, the device of coking wastewater deep treatment reuse technology, this system comprises more medium filter 1, catalytic ozonation reactor 5, ozonizer 13, ozone destruct device 14, middle tank 16, MBR membrane bioreactor 24, cartridge filter 27, reverse osmosis unit 30, the import of more medium filter 1 is connected with water inlet pipe and back flushing water inlet pipe respectively, the outlet of more medium filter 1 is connected with the import of catalytic ozonation reactor 5 and back flushing rising pipe respectively, the outlet of catalytic ozonation reactor 5 is connected with the import of middle tank 16, the ozone input aperture of catalytic ozonation reactor 5 is connected with ozonizer 13 by ozone transport conduit, the ozone delivery port of catalytic ozonation reactor 5 is connected by the import of pipeline with ozone destruct device 14, the outlet of ozone destruct device 14 is connected with the exhaust pipe being provided with tail gas drain 15, the outlet of middle tank 16 is connected with the import of MBR membrane bioreactor 24, and the outlet of MBR membrane bioreactor 24 is connected with the import of cartridge filter 27, and the outlet of cartridge filter 27 is connected with the import of reverse osmosis unit 30, the outlet of reverse osmosis unit 30 is connected with dense water pipe and technological cycle water-cooled tube respectively, cartridge filter 27 top is provided with tensimeter 28, is provided with outer row's mouth 29 bottom cartridge filter 27,
Also comprise air-blaster 22, air-blaster 22 is connected with the bottom of middle tank 16 by the first pneumatic tube being provided with air flowmeter 21, air-blaster 22 is connected with the bottom of MBR membrane bioreactor 24 by the second pneumatic tube being provided with variable valve 23, and middle tank 16 is all connected with sludge treatment pipeline by sludge pump 26 with the mud delivery port of MBR membrane bioreactor 24.
Filtrate in more medium filter 1 is hard coal (Φ 0.5 ~ 2mm), haydite ((Φ 3 ~ 6mm) or quartz sand (Φ 4 ~ 10mm).Catalytic ozonation reactor 5 is vertical tubular structure, tubular structure inside is provided with water distribution board 6, catalyst filling layer 7, filler supporting plate 9 and titanium matter aeration board 10 from top to bottom successively, the top of tubular structure is provided with emergent drain 12, and the outer wall of tubular structure is provided with liquidometer 8.Middle tank 16 inside is provided with the netted baffle plate 17 in top from top to bottom successively, ozone-decomposing agent 18, lower support plate 19 and aerating apparatus 20; Aerating apparatus 20 is titanium matter aeration board.MBR membrane bioreactor 24 adopts immersion MBR membrane bioreactor, and aeration form adopts continuous aeration, and source of the gas adopts air.The entrance end of cartridge filter 27 is provided with chemical feeding points, and the chimney filter material in cartridge filter 27 is any one in pottery, glass sand or plastics; The pore size filter scope of cartridge filter 27 is 0.5 ~ 120 μm.
Principle of work of the present invention is as follows: 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 ozone catalytic efficiency, waste water in catalytic ozonation reactor through the catalytic oxidation of ozone oxidation, catalyzer, produce the hydroxyl radical free radical (OH) that a large amount of oxidisability is extremely strong, 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.Waste water enters MBR membrane bioreactor after the ozone concn in waste water reduces by the effect of aerating apparatus, ozone-decomposing agent in middle tank further, by biological degradation, the crown_interception of high-concentration activated sludge, part water outlet 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.
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; (2) 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, clay, also improves ozone utilising efficiency simultaneously.
Catalytic ozonation reactor is vertical tubular structure, and its top 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 water outlet, titanium matter aeration board.In catalytic ozonation reactor, 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 reactor, filler dosage is 25 ~ 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 reactor lower part should arrange liquidometer, and liquidometer least significant end and water outlet are in same level, and catalytic ozonation reactor lower part water level is higher than water outlet, guarantee that ozone can not overflow from water outlet.Ozonizer can adopt source of the gas air or oxygen.Ozone tail gas breaking plant adopts the breaking plants such as gac absorption, solution absorption.
Middle tank arranges aerating apparatus and ozone-decomposing agent.Aerating apparatus adopts titanium matter aeration board, reduces useless Measuring Ozone Concentration in Water, and increase and ozone-decomposing agent duration of contact, source of the gas adopts air simultaneously.Ozone-decomposing agent adopts transition element metal oxide compound (as: oxide compound of Mn, Cu) as active ingredient, and carrier then adopts γ-Al
2o
3, TiO
2, SiO
2, molecular sieve, several being composited of gac or more.Middle part is provided with ozone-decomposing agent packing layer, ozone-decomposing agent filler dosage is 15 ~ 35% of volume, filler has the netted baffle plate of lower support plate and top to be fixed, also the porous block ozone-decomposing agent filler of sintering can be adopted to lay form, netted baffle plate or back up pad aperture should be less than packing material size, support on the one hand, fix filler, ensure that current pass through on the other hand.
MBR membrane bioreactor adopts immersion MBR membrane bioreactor, and aeration form adopts continuous aeration, and mud adopts the mud of Aerobic Pond backflow in the coke-oven plant's biochemical treatment process after domestication.Source of the gas adopts air.A MBR water outlet part can be used as inferior grade water, as the froth breaking water in biological process, coal yard dust suppression etc.;
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 move to import and export differential water pressures reach 0.1MPa time, should more renew cartridge.Its object is used for the subtitle substance of filtering after MBR (as suspended substance; fine particle etc.); to guarantee that water filtration precision and protection postorder film filtering element be not by the damage of large particulate matter, extends the reverse osmosis unit life-span, meet the normal operation of reverse osmosis system.
Reverse osmosis unit adopts modularized equipment.Object is to the further advanced treatment desalination of waste water, removal 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.
Working process of the present invention is as follows: enter more medium filter 1 by the suspended substance filtrate removal waste water from mixed heavy pond coking chemical waste water out, be beneficial to simultaneously and improve postorder ozone catalytic efficiency, waste water in catalytic ozonation reactor 5 through the catalytic oxidation of ozone oxidation, catalyst filling 7, produce the hydroxyl radical free radical (OH) that a large amount of oxidisability is extremely strong, 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 14.Waste water is ozone-decomposing agent 19 in middle tank 16, effect such as aerating apparatus 20 grade enters MBR membrane bioreactor 24 after being reduced by the ozone concn in waste water further, by biological degradation, the crown_interception of high-concentration activated sludge, part water outlet 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 27, reverse osmosis system 30 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.
Fig. 2 is that this patent embodiment adopts catalytic ozonation reactor.Catalytic ozonation reactor 5 is entered by pump 3 from the water inlet of more medium filter 1, catalytic ozonation reactor 5 is vertical tubular structure, its top is provided with water distribution board 6, emergent drain 12, ozone destruct device 14 and tail gas drain 15, middle part is provided with catalyst filling layer 7 and filler supporting plate 9, and bottom is provided with liquidometer 8, titanium matter aeration board 10.In catalytic ozonation reactor, filler 7 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.In catalytic ozonation reactor 5, filler 7 dosage is 25 ~ 60% of volume; 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.Catalytic ozonation reactor 5 bottom should arrange liquidometer 8, and liquidometer 8 least significant end and water outlet are in same level, and catalytic ozonation reactor 5 bottom water level is higher than water outlet, guarantees that ozone can not overflow from water outlet.Catalytic ozonation reactor filler back up pad air vent aperture is 1mm-2mm, and the material of back up pad is titanium plate.Ozonation aerated device 10 adopts titanium matter aerator.Ozonizer 13 source of the gas can adopt air or oxygen.Ozone tail gas breaking plant 14 adopts the rear emptying of the process such as gac absorption, solution absorption.
Fig. 3 is the middle tank schematic diagram that this patent embodiment adopts.Waste water is after catalyzed oxidation in catalytic ozonation reactor 5, and most of organism is degraded, but the low concentration ozone still containing 0.1 ~ 1.0mg/L in waste water.For improving postorder biochemical action effect, by middle tank, the ozone concn in waste water need be reduced further, reducing postorder biological damage.Middle tank 16 aerating apparatus 20 adopts titanium matter aeration board, and source of the gas adopts air.Ozone-decomposing agent packing layer 18 adopts transition element metal oxide compound (as: oxide compound of Mn, Cu) as active ingredient, and carrier then adopts γ-Al
2o
3, TiO
2, SiO
2, molecular sieve, several being composited of gac or more.Ozone-decomposing agent filler dosage is 15 ~ 35% of volume, filler has the netted baffle plate 17 of lower support plate 19 and top to be fixed, also the porous block ozone-decomposing agent filler of sintering can be adopted to lay form, netted baffle plate or back up pad aperture should be less than packing material size, support on the one hand, fix filler, ensure that current pass through on the other hand.Mud in middle tank and postorder MBR pond is sucked by residual sea water pump 26 and is discharged to sludge sump, and after digestion, machinery is drawn and dug outward transport.Waste water, after middle tank 16, enters the further biochemical degradation of MBR bio-reactor, water outlet reuse after cartridge filter and reverse osmosis unit advanced treatment.
Fig. 4 is in the invention process process, the UV scanning curve before and after Treatment of Coking Effluent.As can be seen from Fig. 4 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.
Immersion MBR device 24, cartridge filter 27 and reverse osmosis unit 30 in the present embodiment with reference to Practical Project operation scheme, can not repeat at this one by one.
Claims (10)
1. a coking wastewater deep treatment reuse technology, is characterized in that: it comprises the steps:
(1) waste water is delivered in mixed heavy pond and carry out precipitation process, the coking chemical waste water after being precipitated;
(2) be delivered to more medium filter from mixed heavy pond coking chemical waste water out and carry out filtration treatment, to reduce the content of the suspended substance in waste water further;
(3) coking chemical waste water after filtering is delivered in catalytic ozonation reactor and carries out ozone oxidation, catalyst oxidizing reaction, make the oxidation of organic substance by hydroxyl radical free radical of bio-refractory in coking chemical waste water, larger molecular organics in waste water and arene compound are degraded into small molecules or CO
2and water; Meanwhile, the residual ozone of effusion enters ozone destruct device;
(4) waste water after oxidation is delivered in middle tank, MBR membrane bioreactor is delivered to after being reduced by ozone concn in waste water further by the effect of aerating apparatus, ozone-decomposing agent in middle tank, by biological degradation, the crown_interception of high-concentration activated sludge, to the further biochemical degradation of micromolecular compound, also retain partial suspended thing simultaneously;
(5) waste water out from MBR membrane bioreactor is directly used as defoamer use water, coal yard dust suppression and reclaimed water in biological process; Or:
(6) waste water out from MBR membrane bioreactor is delivered to further filtration treatment in cartridge filter, filtering is partial suspended thing wherein;
(7) waste water after security personnel filter is delivered in reverse osmosis unit and carries out further desalination, gained desalination waste water recycling makes technique recirculated cooling water, and reverse osmosis dense water is out as blast-furnace slag cooling flushing cinder water, coal yard dust suppression water, road-cleaning water.
2. coking wastewater deep treatment reuse technology according to claim 1, is characterized in that: in described step (3), in catalytic ozonation reactor, filler is burned diatomite, haydite or gac, and packing specific area is greater than 200m
2/ m
3; In catalytic ozonation reactor, filler dosage is 25 ~ 60% of catalytic ozonation reactor volume; Ozonizer source of the gas adopts air or oxygen.
3. coking wastewater deep treatment reuse technology according to claim 1, is characterized in that: in described step (4), middle tank arranges aerating apparatus and ozone-decomposing agent; Aerating apparatus adopts titanium matter aeration board, and source of the gas adopts air; Smelly decomposition agent adopts the oxide compound of Mn, Cu as active ingredient, and carrier adopts γ-Al
2o
3, TiO
2, SiO
2, several mixture of molecular sieve, gac or more; Ozone-decomposing agent filler dosage is 15 ~ 35% of middle tank volume.
4. coking wastewater deep treatment reuse technology according to claim 1, is characterized in that: in described step (6), and the chimney filter material of cartridge filter is pottery, glass sand or plastics; Pore size filter is 0.5 ~ 120 μm; Be provided with chemical feeding points before described cartridge filter, add clorox sterilant and sodium bisulfite respectively as reductive agent.
5. one kind for realizing the coking wastewater deep treatment reclamation set that technique described in claim 1 designs, comprise more medium filter (1), catalytic ozonation reactor (5), ozonizer (13), ozone destruct device (14), middle tank (16), MBR membrane bioreactor (24), cartridge filter (27), reverse osmosis unit (30), is characterized in that:
The import of described more medium filter (1) is connected with water inlet pipe and back flushing water inlet pipe respectively, the outlet of more medium filter (1) is connected with the import of catalytic ozonation reactor (5) and back flushing rising pipe respectively, the outlet of catalytic ozonation reactor (5) is connected with the import of middle tank (16), the ozone input aperture of catalytic ozonation reactor (5) is connected with ozonizer (13) by ozone transport conduit, the ozone delivery port of catalytic ozonation reactor (5) is connected by the import of pipeline with ozone destruct device (14), the outlet of ozone destruct device (14) is connected with the exhaust pipe being provided with tail gas drain (15), the outlet of middle tank (16) is connected with the import of MBR membrane bioreactor (24), the outlet of MBR membrane bioreactor (24) is connected with the import of cartridge filter (27), and the outlet of cartridge filter (27) is connected with the import of reverse osmosis unit (30), the outlet of reverse osmosis unit (30) is connected with dense water pipe and technological cycle water-cooled tube respectively, cartridge filter (27) top is provided with tensimeter (28), and cartridge filter (27) bottom is provided with outer row's mouth (29),
Also comprise air-blaster (22), air-blaster (22) is connected with the bottom of middle tank (16) by the first pneumatic tube being provided with air flowmeter (21), air-blaster (22) is connected with the bottom of MBR membrane bioreactor (24) by the second pneumatic tube being provided with variable valve (23), and middle tank (16) is all connected with sludge treatment pipeline by sludge pump (26) with the mud delivery port of MBR membrane bioreactor (24).
6. coking wastewater deep treatment reclamation set according to claim 5, is characterized in that: the filtrate in described more medium filter (1) is the quartz sand of the hard coal of particle diameter Φ 0.5 ~ 2mm, the haydite of particle diameter Φ 3 ~ 6mm or particle diameter Φ 4 ~ 10mm.
7. coking wastewater deep treatment reclamation set according to claim 5, it is characterized in that: described catalytic ozonation reactor (5) is vertical tubular structure, tubular structure inside is provided with water distribution board (6), catalyst filling layer (7), filler supporting plate (9) and titanium matter aeration board (10) from top to bottom successively, the top of tubular structure is provided with emergent drain (12), and the outer wall of tubular structure is provided with liquidometer (8).
8. coking wastewater deep treatment reclamation set according to claim 5, it is characterized in that: described middle tank (16) inside is provided with the netted baffle plate in top (17) from top to bottom successively, ozone-decomposing agent (18), lower support plate (19) and aerating apparatus (20); Described aerating apparatus (20) is titanium matter aeration board.
9. coking wastewater deep treatment reclamation set according to claim 5, is characterized in that: described MBR membrane bioreactor (24) adopts immersion MBR membrane bioreactor, and aeration form adopts continuous aeration, and source of the gas adopts air.
10. coking wastewater deep treatment reclamation set according to claim 5, it is characterized in that: the entrance end of described cartridge filter (27) is provided with chemical feeding points, the chimney filter material in cartridge filter (27) is any one in pottery, glass sand or plastics; The pore size filter scope of cartridge filter (27) is 0.5 ~ 120 μm.
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