Summary of the invention
Goal of the invention: the invention aims to solve the deficiencies in the prior art, it is provided that a kind of process optimization is rationally, persistent organic pollutants treatment effeciency is high, treatment effect is stable and the process of the chemical wastewater treatment of economical rationality.
Technical scheme:
In order to realize the purpose of the present invention, the technical solution used in the present invention is: IFBR-UASB-A/OBR processes wastewater from chemical industry group technology, and this group technology is that wastewater from chemical industry is processed by combination modified model Fenton fluid bed (IFBR), up-flow anaerobic sludge blanket (UASB) and aerobic/anaerobic baffled reactor (A/OBR);Group technology includes balancing tank, modified model Fenton fluid bed, degassing neutralization pond, coagulative precipitation tank, up-flow anaerobic sludge blanket, aerobic/anaerobic baffled reactor, is sequentially connected with through water pipe.
This technique includes following operating procedure:
(1) wastewater from chemical industry is after pretreatment, enters balancing tank;
(2) it is adjusted rear waste water and is conveyed into modified model Fenton fluid bed by intake pump, in modified model Fenton fluid bed, be separately added into H by medicine system2SO4Solution, FeSO4Solution and H2O2Solution, is entered part effluent recycling in modified model Fenton fluid bed by reflux pump, presents fluidisation state in making Fenton fluid bed;
Modified model Fenton fluid bed oxidation tower body is cylindrical shape, and three pieces of sieve plates are divided into oxidizing tower from bottom to top into water water distribution area, Fenton oxidation district, ferrum carbon reaction zone and exhalant region;Fenton oxidation district is added with filler A, and ferrum carbon reaction zone is added with filler B;Circulating device is connected to tower body water inlet at outlet and two;By Fenton's reaction and the micro-electrolysis reaction of ferrum carbon reaction zone in Fenton oxidation district, remove part COD and most persistent organic pollutants in waste water;
(3) water outlet of modified model Fenton fluid bed enters degassing neutralization pond, sloughs a small amount of gas by stirring, adds NaOH solution, the pH value of regulation waste water;
(4) degassing neutralization pond water outlet enters coagulative precipitation tank, adds coagulant by coagulant medicine system, and controls mixing speed and form big flco;Entering back into sediment fraction, the big flco of formation realizes precipitate and separate in settling zone, and precipitating sludge processes through sludge treating system;
(5) coagulative precipitation tank water outlet enters up-flow anaerobic sludge blanket through infusion, after waste water is entered by reactor lower part, pass upward through Sludge Bed district, suspended sludge area, three phase separator, then draining, remove part COD and persistent organic pollutants in waste water by the effect of anaerobe, reduce the SS of waste water further;The time of staying is 12~36 h;
(6) up-flow anaerobic sludge blanket water outlet enters aerobic/anaerobic baffled reactor, first utilizes anaerobe to carry out anaerobic bio-treated in anaerobism section, and anaerobism section uses box-cage type ABR reactor;Waste water is deflected into aerobic section (OBR) subsequently, makes good use of oxygen animalcule and carries out Aerobic biological process, and aerobic section uses baffling pattern, arranges aerator at concrete conversion zone so that dissolved oxygen therein is more than 2.0
mg/L;
(7) the waste water water outlet after sedimentation in secondary sedimentation tank after aerobic/anaerobic baffled reactor processes.
Further, the bottom of balancing tank is provided with microporous aeration device, the water quality and quantity of regulation waste water;Wastewater from chemical industry water quality index after regulation: COD be 5000 ~ 6000 mg/L, SS be 150~300mg/L, chlorobenzene class is 60 ~ 80 mg/L.
Further, the filler A of modified model Fenton fluid bed uses quartz sand, and particle diameter is 0.5 ~ 1.5
Mm, the filler B that ferrum carbon reaction zone is arranged, use active carbon fiber felt;First use liquid phase reduction to load zeroth order Nanoscale Iron on active carbon fiber felt, refill and insert ferrum carbon reaction zone;Active carbon fiber felt, is placed in netted intersection between upper strata sieve plate and middle sieve plate.
Further, the exhalant region of modified model Fenton fluid bed connects circulating device, divides two water inlet pipes to be respectively fed to bottom and the bottom of ferrum carbon reaction zone in Fenton oxidation district, and the backflow water yield is respectively Q1And Q2, Q1With Q2Ratio with m3/ d meter ratio is 8:1-10:1.
Further, during modified model Fenton fluidized bed processing, H2O2It is 2 ~ 4:1, H with COD ratio in terms of mg/L2O2With Fe2+Mol ratio be 3 ~ 5:1, the waste water mean residence time in Fenton oxidation district controls at 0.5 ~ 1.5 hour, the waste water mean residence time in ferrum carbon reaction zone controls at 15 ~ 45 minutes, the pH value of waste water in Fenton fluid bed is regulated so that it is maintain between 3.0 ~ 4.0 by medicine system and online pH meter.
Further, the design volumetric loading of up-flow anaerobic sludge blanket is 10 ~ 12 kgBOD/(kg MLSS d).
Further, the anaerobism section of aerobic/anaerobic baffled reactor uses box-cage type ABR reactor, box-cage type ABR reactor is made up of 3~6 compartments, each compartment includes upward flow compartment and lower to stream compartment, upward flow compartment and the lower volumetric ratio to stream compartment are 3~5:1, be provided with boxes and baskets, load filler in boxes and baskets in upward flow compartment, being provided with actuating device at compartment top, actuating device is connected with boxes and baskets by cable wire.
Further, box-cage type ABR reactor, boxes and baskets are made up of rustless steel grizzly bar, for rectangular shape;The length and width of boxes and baskets is respectively less than the length and width of upward flow compartment, and height is the 35~50% of upward flow compartment effective depth, and the wall of boxes and baskets and upward flow compartment is at a distance of less than 5mm;Size of mesh opening between rustless steel grizzly bar is less than the minimum dimension of filler;Filler is floating stuffing, and density is at 0.90~0.96 g/cm3, filler diameter 10~25mm, material is polypropylene or polyethylene.
Further, the startup method of box-cage type ABR reactor is to be seeded to by seed sludge in above-mentioned box-cage type ABR reactor, pumps into the treatment sewage being heated to 35 DEG C, and the concentration making mud is 10~15 g/L, boxes and baskets are filled filler again, and the hydraulic detention time in regulation reactor is 6~24h;Boxes and baskets are placed in upward flow compartment bottom by initial start stage, after upward flow compartment bottom suspension anaerobic sludge and biomembranous amount increase, enter mid-term;Start mid-term, boxes and baskets are placed in the middle part of upward flow compartment, after suspension anaerobic sludge in the middle part of upward flow compartment and biomembranous amount increase, enter the later stage;Starting the later stage, boxes and baskets being placed in upward flow compartment top, until having started;Initial start stage, the time in mid-term and startup later stage that starts distribute in terms of sky, and ratio is 3:4:5,3:5:4,5:4:4 or 5:4:3.
Ultimate principle is summarized as follows.
1, IFBR(modified model Fenton fluid bed) operation principle
(1) waste water enters the Fenton oxidation district of modified model Fenton fluid bed, is separately added into H by medicine system in Fenton fluid bed simultaneously2SO4Solution, FeSO4Solution and H2O2Solution, by reflux pump, water part is flowed back in Fenton fluid bed, fluidisation state is presented in making Fenton fluid bed, part COD and the organic pollution (being i.e. difficult to biodegradable organic pollution, also known as characteristic contamination or characteristic organic pollutants) of most difficult degradation of waste water is removed by Fenton's reaction;Regulation return flow, controls the height of filler expansion less than middle sieve plate.
The principle of Fenton fluidized bed process: utilizing carrier is to be entered into and up flowing by Fenton fluidized-bed bottom as crystallization nuclear species, pending waste water and interpolation medicament.Be circumscribed with effluent recycling pipeline, in order to adjust influent stream water degree of supersaturation and reach Flow Velocity on carrier make carrier surface formed stable state crystalline solid, when crystal particle diameter reaches 2.5
After the mm of mm ~ 3, outside drain tank, carry out recycling.Fenton fluidized bed process utilizes the pattern of fluid bed to make ferric iron major part produced by Fenton method be crystallized or precipitate, and is coated on the carrier surface of liquid bed, is one and combines homophase chemical oxidation (Fenton method), out-phase chemical oxidation (H2O2/ FeOOH), the new technique of the function such as fluid bed crystallization.Traditional Fenton oxidation method has been made significantly to improve by this technology, so can reduce employing traditional F enton method and produce substantial amounts of chemical sludge, the iron oxides simultaneously formed at carrier surface has the effect of heterocatalysis, and the pattern of fluid bed also promotes chemical oxidation reaction and mass-transfer efficiency, COD clearance is made to promote.Its reacted go out flowing water through pH value adjust after can produce iron containing sludge.Iron containing sludge reduces 70% than traditional Fenton oxidation, also reduces H2O2The waste of medication, may utilize hydrogen peroxide chemical feeding quantity simultaneously and adjusts, adjust COD removal amount, it is achieved effectively control the reduction of the COD of waste water, is the guarantee of waste water process qualified discharge.Fenton process is as the one of advanced oxidation simultaneously, the present invention mainly utilizes Fenton process to be difficult to biodegradable organic pollution except the most of waste water, make persistent organic pollutants chain rupture, open loop efficiently, resolve into small organic molecule, improve the biodegradability of waste water, it is easy to be further processed at follow-up biological processing unit.
(2) waste water enters the ferrum carbon reaction zone of modified model Fenton fluid bed through middle sieve plate, under the conditions of iron-carbon micro-electrolysis, and persistent organic pollutants in catalysis oxidized waste water.Micro electrolysis tech is a kind of ideal technology processing high concentrated organic wastewater at present.It is in the case of cold, and the potential difference utilizing the micro-electrolysis material self being filled in waste water to produce carries out electrolysis process to waste water, to reach the purpose of degradable organic pollutant.Middle sieve plate plays support ferrum carbon reaction zone filler and the effect of rectification.Modified model Fenton fluid bed, mainly by the zeroth order Nanoscale Iron of activated carbon fiber Yu load, forms the ferrum carbon battery of light electrolysis.The potential difference utilizing the micro-electrolysis material self being filled in waste water to produce carries out electrolysis process, the organic substance in catalytic degradation waste water to waste water.Active carbon fiber felt, after the zeroth order Nanoscale Iron of load consumes, takes out fiber felt, regenerates with liquid phase reduction, recycled.
2, UASB operation principle
Upflow anaerobic sludge blanket reactor (UASB) anaerobic reaction process, as other Anaerobic treatment techniques, including hydrolysis, acidifying, produces acetic acid and methane phase etc..Participate in the conversion process of substrate by different microorganisms and convert a substrate into the inorganic matters such as end product natural pond gas and water.UASB is made up of sludge reaction district, gas-liquid-solid three-phase separator (including settling zone) and air chamber three part.Sewage passes through from bottom to top, and reactor bottom has a high concentration, highly active Sludge Bed, and the majority of organic pollutants in sewage is degraded to methane and carbon dioxide through anaerobic fermentation here.These anaerobic processes are proper absolute anaerobic processes, and biological agent process does not has oxygen to participate in, and the anaerobe of cultivation is preponderated.Anaerobe forms granule sludge and the organic pollution of COD in waste water and difficult degradation plays main removal effect, and removal efficiency is high.Because of current and the agitation of bubble, on Sludge Bed, there is a sludge suspension layer.Reactor top is provided with three phase separator, in order to separating digesting gas, Digestive system and mud granule.Digestion gas autoreactor top is derived;The automatic landing of mud granule is settled down to the Sludge Bed of reactor bottom;Digestive system is from settling section water outlet.
UASB load-bearing capacity is the biggest, it is adaptable to high concentrated organic wastewater, the process of such as wastewater from chemical industry.The UASB of operational excellence has the highest organic pollutant removal rate, it is not necessary to stirring, adapts to load impact by a relatively large margin, temperature and pH change.The basic feature of UASB reactor is without absorption carrier, just can form the granule sludge that settling property is good, the speck of high concentration in holding reactor, thus can bear higher COD load, and COD clearance is up to more than 90%.Compared with other anaerobic biological reactors, the feature of UASB: (1) simple structure is ingenious, can turn out anaerobic grain sludge in reactor, it is achieved that mud mud age (SRT) separates with hydraulic detention time (HRT), thus Biomass is many in Sludge Bed, equivalent concentration calculates up to 20 ~ 30g/L;(2) volumetric loading rate is high, under the conditions of mesophilic digestion, typically up to 10kgCOD/(m d) left and right, waste water hydraulic detention time in reactor is shorter, and therefore required pond appearance is substantially reduced.(3) UASB reactor has the biggest adaptability to all kinds of waste water, and energy consumption is low, and sludge output is few.Weak point is to remove the nitrogen in waste water and phosphorus.
3, A/OBR operation principle
Aerobic/anaerobic baffled reactor is made up of with aerobic section (OBR, aerobic deflector type reaction zone) anaerobism section box-cage type ABR reactor.
In the upward flow compartment of box-cage type ABR reactor, boxes and baskets are set, filler is loaded in boxes and baskets, on compartment side, actuating device is set, move up or down boxes and baskets, it is formed with the moving bed of packing layer, pending waste water is entered reactor by water inlet, sequentially passes through compartment, after treatment by outlet water outlet.On the basis of tradition ABR reactor, in conjunction with moving bed biological membrane technology, and in order to make the position of moving bed and run controlled, add the actuating device on boxes and baskets and compartment top.Filler is added in the upward flow compartment of reactor, purpose seeks to hang biomembrane on filler, forms anaerobism suspended sludge and biomembrane synergy, increases sludge concentration in reactor generally, make reactor can bear higher COD and process load, improve biological treatment efficiency.
The setting of boxes and baskets and control so that during whole Primary culture, filler is fully contacted with seed sludge in ABR, thus serves the effect of the start-up course accelerating ABR, it is achieved shorten the effect of startup time.The grizzly bar grid at boxes and baskets top plays the effect retaining filler, does not allow filler be lost to next compartment;Boxes and baskets packing layer occupy to stream compartment top when simultaneously, also has crown_interception to suspension anaerobic sludge, reduces number of dropouts, maintain high suspended sludge concentration, improves biological treatment efficiency.Aerobic deflector type reaction zone is provided with the biofilm filler of suspension, uses biotechnology, screens, tames and constructs to degrade and common are the dominant microflora of machine characteristic contamination in wastewater from chemical industry, and dominant microflora is fixed on aerobic zone.Keep the high Biomass of aerobic deflector type reaction zone, thus improve biological treatment efficiency.
The process of the present invention is suitable for the process of the industrial wastewater of the organic properties pollutant containing difficult degradation such as wastewater from chemical industry, and in waste water, the total removal rate of the organic pollution of COD and difficult degradation is more than 95%, and effluent quality can meet the requirement in environmental protection.
Beneficial effect: beneficial effects of the present invention is as follows compared with existing technique.
1, the invention provides the group technology of a kind of different design.
2, process optimization, clear route is succinct;Bio-chemical effluent is through materializing strategy (modified model Fenton fluid bed IFBR), carry out biochemical treatment (the UASB reactor of absolute anaerobism+box-cage type ABR reactor+OBR Aerobic biological process) again, last water outlet after precipitation, technique composition is rationally, biochemical treatment and materializing strategy the most organically being combined, three main bodys processing unit IFBR, UASB and A/OBR mutually support.
3, general wastewater from chemical industry can effectively be processed by the technique that the present invention provides, and can obtain good treatment effect, meet the requirement in environmental protection.The technique that the present invention provides, overall COD clearance >=95%, organic properties pollutants removal rate >=95%, operational management is convenient, process stabilizing, and investment operating cost is low.Overcoming processing cost high, persistent organic pollutants are inefficient, and process operation is unstable, and treatment effect is undesirable, it is impossible to meet the deficiencies such as environmental requirement.
4, the technique that the present invention provides, the wherein homophase of Fenton fluid bed and the catalytic reaction of out-phase, the iron containing sludge of generation, than traditional Fenton oxidation minimizing 70%, also reduces H2O2The waste of medication, may utilize hydrogen peroxide chemical feeding quantity simultaneously and adjusts, adjust COD removal amount, it is achieved effectively control the reduction of the COD of waste water, ensure effluent quality.Being organically combined with micro-electrolysis reaction by Fenton oxidation of modified model Fenton fluid bed, makes persistent organic pollutants chain rupture, open loop the most efficiently, resolves into small organic molecule.Compared with the common Fenton fluid bed of co-content and treating capacity, in the case of water inlet indices is identical with added pharmaceutical quantities, the clearance of the organic pollution of difficult for biological degradation can be improved 10%, improve the biodegradability of waste water further.
Embodiment 1:
Certain Production in Chemical Plant process synthesis waste water, belongs to high concentrated organic wastewater, influent concentration COD before treatment≤6000mg/L, pH 6.5~8.5, SS≤300mg/L, NH3-N≤100mg/L,
TP≤5mg/L, characteristic contamination concentration chlorobenzene class≤80mg/L.Water outlet requires to reach " the main pollution discharge standard of Chemical Industry in Jiangsu Province " (DB32/939-2006) secondary standard.Effluent index requires COD≤120mg/L, pH 6.5~8.5, SS≤150mg/L, NH3-N≤25mg/L, TP≤1.0mg/L, characteristic contamination concentration chlorobenzene class≤1.0 mg/L.
Wastewater from chemical industry is processed by the group technology using modified model Fenton fluid bed (IFBR), up-flow anaerobic sludge blanket (UASB) and the aerobic/anaerobic baffled reactor (A/OBR) of present invention offer;Including balancing tank, modified model Fenton fluid bed, degassing neutralization pond, coagulative precipitation tank, up-flow anaerobic sludge blanket, aerobic/anaerobic baffled reactor, it is sequentially connected with through water pipe.
This technique includes following operating procedure:
(1) wastewater from chemical industry is after pretreatment, enters balancing tank;
(2) it is adjusted rear waste water and is conveyed into modified model Fenton fluid bed by intake pump, in modified model Fenton fluid bed, be separately added into H by medicine system2SO4Solution, FeSO4Solution and H2O2Solution, is entered part effluent recycling in modified model Fenton fluid bed by reflux pump, presents fluidisation state in making Fenton fluid bed;
Modified model Fenton fluid bed oxidation tower body is cylindrical shape, and three pieces of sieve plates are divided into oxidizing tower from bottom to top into water water distribution area, Fenton oxidation district, ferrum carbon reaction zone and exhalant region;Fenton oxidation district is added with filler A, and ferrum carbon reaction zone is added with filler B;Circulating device is connected to tower body water inlet at outlet and two;By Fenton's reaction and the micro-electrolysis reaction of ferrum carbon reaction zone in Fenton oxidation district, remove part COD and most persistent organic pollutants in waste water;
(3) water outlet of modified model Fenton fluid bed enters degassing neutralization pond, sloughs a small amount of gas by stirring, adds NaOH solution, the pH value of regulation waste water;
(4) degassing neutralization pond water outlet enters coagulative precipitation tank, adds coagulant by coagulant medicine system, and controls mixing speed and form big flco;Entering back into sediment fraction, the big flco of formation realizes precipitate and separate in settling zone, and precipitating sludge processes through sludge treating system;
(5) coagulative precipitation tank water outlet enters up-flow anaerobic sludge blanket through infusion, after waste water is entered by reactor lower part, pass upward through Sludge Bed district, suspended sludge area, three phase separator, then draining, remove part COD and persistent organic pollutants in waste water by the effect of anaerobe, reduce the SS of waste water further;The time of staying is 24 h;
(6) up-flow anaerobic sludge blanket water outlet enters aerobic/anaerobic baffled reactor, first utilizes anaerobe to carry out anaerobic bio-treated in anaerobism section, and anaerobism section uses box-cage type ABR reactor;Waste water is deflected into aerobic section (OBR) subsequently, makes good use of oxygen animalcule and carries out Aerobic biological process, and aerobic section uses baffling pattern, arranges aerator at concrete conversion zone so that dissolved oxygen therein is more than 2.0
mg/L;
(7) the waste water water outlet after sedimentation in secondary sedimentation tank after aerobic/anaerobic baffled reactor processes.
Waste water is conveyed into Fenton fluid bed inhalant region through intake pump, by bottom sieve plate water distribution;Waste water enters Fenton fluid bed Fenton oxidation district, is separately added into H by medicine system in Fenton fluid bed simultaneously2SO4Solution, FeSO4Solution and H2O2Solution, is flowed back into the water section in effluent trough in Fenton fluid bed by reflux pump, presents fluidisation state in making Fenton fluid bed, removes part COD and major part chlorobenzene class organic pollution in waste water by Fenton's reaction;Regulation return flow, controls the height of filler expansion less than middle sieve plate;Waste water enters ferrum carbon reaction zone through middle sieve plate, under the conditions of iron-carbon micro-electrolysis, and persistent organic pollutants in catalysis oxidized waste water;The waste water aoxidized through iron-carbon micro-electrolysis catalysis passes through upper strata sieve plate, in effluent weir enters effluent trough, enters next processing unit by outlet pipe;Top effluent trough connects circulating device, divides two water inlet pipes to be respectively fed to bottom and the bottom of ferrum carbon reaction zone in Fenton oxidation district, flow back into discharge and be respectively Q1And Q2, Q1With Q2With m3/ d meter ratio is 8:1.
During Fenton fluidized bed processing, H2O2It is 2.5:1, H with concentration ratio (mg/L) of COD2O2With Fe2+Mol ratio be 4:1, the waste water mean residence time in Fenton oxidation district controls at 1 hour, the waste water mean residence time in ferrum carbon reaction zone controls at 30 minutes, regulates the pH value of waste water in Fenton fluid bed by medicine system and online pH meter, makes pH value maintain between 3.0~4.0.
Up-flow anaerobic sludge blanket, design volumetric loading is 11 kgBOD/(kg
MLSS d).
Box-cage type moving bed modified model ABR reactor, it is made up of 4 compartments, each compartment is divided into again upward flow compartment and lower to flowing compartment, and upward flow compartment and the lower ratio to the volume of stream compartment are 3:1, wherein, in upward flow compartment, boxes and baskets are set, loading filler in boxes and baskets, be provided with actuating device at upward flow compartment top, actuating device is connected with boxes and baskets by cable wire, boxes and baskets can be controlled move up or down, be formed with the moving bed of packing layer.It is provided with backflow recoil tube bottom upward flow compartment, sequentially passes through 4 compartments, after treatment water outlets.Boxes and baskets are made up of rustless steel grizzly bar, and in rectangular shape, the length and width of boxes and baskets is slightly less than the length and width of upward flow compartment, and height is the 35% of the effective depth of upward flow compartment 4.Filling up filler in boxes and baskets, filler uses Kaldnes floating stuffing, and density is 0.95 g/cm3, a diameter of 10mm of filler, material is polyethylene.
The startup method of box-cage type ABR reactor is to be seeded to by seed sludge in above-mentioned box-cage type ABR reactor, pump into the treatment sewage being heated to 35 DEG C, the concentration making mud is 15 g/L, again boxes and baskets are filled filler, initial start stage, boxes and baskets are placed in upward flow compartment bottom, after upward flow compartment bottom suspension anaerobic sludge and biomembranous amount increase, enter mid-term;Start mid-term, boxes and baskets are placed in the middle part of upward flow compartment, after suspension anaerobic sludge in the middle part of upward flow compartment and biomembranous amount increase, enter the later stage;Starting the later stage, boxes and baskets being placed in upward flow compartment top, until having started;Initial start stage, the time in mid-term and startup later stage that starts distribute in terms of sky, and ratio is 5:4:4.The hydraulic detention time controlled in reactor is 12~18h;Influent COD is progressively upgraded to 1000mg/L, and the hydraulic detention time controlled in reactor is 18h, gradually reduces hydraulic detention time to 12h.
After combined PROCESS FOR TREATMENT, effluent index COD≤80mg/L, pH 6.5~8.5, SS≤50mg/L, NH3-N≤20mg/L, TP≤1.0mg/L, characteristic contamination concentration chlorobenzene class≤0.8mg/L.Leading indicator each unit treatment effect see table.
Table 1 leading indicator each unit treatment effect catalog