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 closes
Reason, persistent organic pollutants treatment effeciency are high, treatment effect is stable and the process of the Industrial 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-ICEAS
Processing industrial wastewater novel process, this technique is that modified model Fenton fluid bed (IFBR), up-flow anaerobic sludge blanket are used in combination
(UASB) with ICEAS reactor, industrial wastewater is processed;Group technology includes regulating reservoir, modified model Fenton fluid bed, takes off
Gas neutralization pond, coagulative precipitation tank, up-flow anaerobic sludge blanket and ICEAS reactor, be sequentially connected with through water pipe.
The technique of this process industrial wastewater includes following operating procedure:
(1) industrial wastewater is after pretreatment, enters regulating reservoir;
(2) it is adjusted rear waste water and is conveyed into modified model Fenton fluid bed by intake pump, by medicine system to modified model Fenton stream
Change in bed and be separately added into H2SO4Solution, FeSO4Solution and H2O2Solution, enters modified model by reflux pump fragrant by part effluent recycling
Pause in fluid bed, in making Fenton fluid bed, present fluidisation state;The oxidizing tower of modified model Fenton fluid bed is cylindrical shape, three pieces of sieve plates
Oxidizing tower is divided into 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 filling out
Material A, ferrum carbon reaction zone is added with filler B;Circulating device is connected to water inlet at the two of exhalant region and oxidizing tower;Pass through Fenton oxidation
The Fenton's reaction in district and the micro-electrolysis reaction of ferrum carbon reaction zone, remove part COD and the organic dirt of most difficult degradation in waste water
Dye thing;
(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 stirring speed
Degree forms big flco;Entering back into sediment fraction, the big flco of formation realizes precipitate and separate, precipitating sludge warp in settling zone
Sludge treating system processes;
(5) coagulative precipitation tank water outlet enters up-flow anaerobic sludge blanket through infusion, after waste water is entered by reactor lower part, passes upward through
Sludge Bed district, suspended sludge area, three phase separator, then water outlet, biogas is discharged by air chamber;By the effect of anaerobe
Remove part COD and persistent organic pollutants in waste water, reduce the SS of waste water further;Control hydraulic detention time be 12~
36 h;Sludge Bed district granule sludge is tamed by anaerobic sludge;
(6) up-flow anaerobic sludge blanket water outlet enters ICEAS reactor, and reactor is designed as two parts along pond length direction, anterior
Being also referred to as pre-reaction zone for biological selecting area, rear portion is main reaction region;The aeration of main reaction region, precipitation, draining, the process week such as idle
Phase circular flow;Pre-reaction zone arranges micro-aerator, and the water decanter of liftable draining is installed at rear portion, main reaction region;Realize simultaneously
Continuum micromeehanics, is interrupted draining;
(7) discharged wastewater met the national standard after ICEAS reactor for treatment.
Further, the bottom of regulating reservoir is provided with microporous aeration device, the water quality and quantity of regulation waste water;Work after being adjusted
Industry waste water quality index: COD be 5000 ~ 6000 mg/L, SS be 150~300mg/L, chlorobenzene class is 60 ~ 80 mg/L.
Further, the filler B that ferrum carbon reaction zone is arranged can use column-shaped active carbon, column-shaped active carbon, and round end diameter 3 ~
4mm, highly 8 ~ 12 mm, first use liquid phase reduction to load zeroth order Nanoscale Iron on the activated carbon, refill and insert ferrum carbon reaction zone,
Refill and insert ferrum carbon reaction zone.
Further, the exhalant region of modified model Fenton fluid bed connects circulating device, and point two water inlet pipes are respectively fed to sweet smell
Water inlet at the two of zoneofoxidation bottom and bottom, ferrum carbon reaction zone, 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/L2O2
With Fe2+Mol ratio be 3 ~ 5:1, the waste water mean residence time in Fenton oxidation district controlled at 0.5 ~ 1.5 hour, and waste water exists
The mean residence time of ferrum carbon reaction zone controls at 15 ~ 45 minutes, regulates Fenton fluid bed by medicine system and online pH meter
The pH value of middle waste water so that it is maintain between 3.0 ~ 4.0.
Further, the design volumetric loading of up-flow anaerobic sludge blanket is 10 ~ 12 kgCOD/(m3D).
Further, the aeration of ICEAS reactor main reaction region, precipitation, draining, the process cycle period such as idle are 4 little
Time, aeration, precipitation, draining, the distribution of idle time are respectively 120 minutes, 60 minutes, 40 minutes, 20 minutes;Reactor runs
Sludge loading is 0.15 ~ 0.35 kgCOD/(kgMLSS d).
Ultimate principle is summarized as follows.
1, modified model Fenton fluid bed (IFBR) operation principle
(1) waste water enters the Fenton oxidation district of modified model Fenton fluid bed, is divided in Fenton fluid bed by medicine system simultaneously
Do not add H2SO4Solution, FeSO4Solution and H2O2Solution, is flowed back into water part in Fenton fluid bed by reflux pump, makes
Present fluidisation state in Fenton fluid bed, removed part COD and organic dirt of most difficult degradation of waste water by Fenton's reaction
Dye thing (being i.e. difficult to biodegradable organic pollution, also known as characteristic contamination or characteristic organic pollutants);Regulation return flow,
Control the height of filler expansion less than middle sieve plate.
The principle of Fenton fluidized bed process: utilizing carrier is by sweet smell as crystallization nuclear species, pending waste water and interpolation medicament
The fluidized-bed bottom that pauses enters into and up flowing.It is circumscribed with effluent recycling pipeline, in order to adjust influent stream water degree of supersaturation and to reach to carry
On body, Flow Velocity makes carrier surface form stable state crystalline solid, after crystal particle diameter reaches 2.5 mm ~ 3 mm, reclaims outside drain tank
Recycling.Fenton fluidized bed process utilizes the pattern of fluid bed to make ferric iron major part produced by Fenton method be crystallized or heavy
Form sediment, be coated on the carrier surface of liquid bed, be one and combine 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 by this technology
Improvement, so can reduce employing traditional F enton method and produce substantial amounts of chemical sludge, the ferrum oxygen simultaneously formed at carrier surface
Compound has the effect of heterocatalysis, and the pattern of fluid bed also promotes chemical oxidation reaction and mass-transfer efficiency, makes COD remove
Rate promotes.Its reacted go out flowing water through pH value adjust after can produce iron containing sludge.Iron containing sludge reduces than traditional Fenton oxidation
70%, also reduce 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, the present invention simultaneously
Mainly utilize Fenton process to be difficult to biodegradable organic pollution except the most of waste water, make difficult degradation organic efficiently
Pollutant chain rupture, open loop, resolve into small organic molecule, improve the biodegradability of waste water, it is easy at follow-up biological treatment list
Unit is further processed.
(2) waste water enters the ferrum carbon reaction zone of modified model Fenton fluid bed through middle sieve plate, in iron-carbon micro-electrolysis condition
Under, persistent organic pollutants in catalysis oxidized waste water.Micro electrolysis tech is a kind of reason processing high concentrated organic wastewater at present
Think technique.It is in the case of cold, utilizes the potential difference that the micro-electrolysis material self being filled in waste water produces to useless
Water carries out electrolysis process, to reach the purpose of degradable organic pollutant.Middle sieve plate play 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 Yu load, forms the ferrum of light electrolysis
Carbon battery.The potential difference utilizing the micro-electrolysis material self being filled in waste water to produce carries out electrolysis process, catalysis fall to waste water
Solve the organic substance in waste water.After the zeroth order Nanoscale Iron of load consumes, activated carbon is taken out, with liquid phase reduction again
Raw, recycled.
2, upflow anaerobic sludge blanket reactor (UASB) operation principle
Upflow anaerobic sludge blanket reactor (UASB) anaerobic reaction process is as other Anaerobic treatment techniques, including water
Solve, acidifying, produce acetic acid and methane phase etc..Majority of organic pollutants in sewage is degraded to methane through anaerobic fermentation here
And carbon dioxide.These anaerobic processes are proper absolute anaerobic processes, and biological agent process does not has oxygen to participate in, training
The anaerobe supported is preponderated.Anaerobe forms granule sludge and the organic pollution of COD in waste water and difficult degradation rises main removal
Effect, and removal efficiency is high.Upflow anaerobic sludge blanket reactor (UASB) main body is reaction tower, can be divided into into water cloth water system
System, reaction zone (anaerobic granular sludge bed layer), three-phase separation area, outlet system and return-flow system.It is dirty that UASB relies primarily on granule
Mud processes waste water, currently belongs to more advanced anaerobic process.Waste water is entered reactor by the water-locator of bottom, by rich in anaerobism
The mud district of bacterium, under the effect of anaerobe, COD and persistent organic pollutants are removed in a large number, produce a large amount of natural pond simultaneously
Gas, the effect by three phase separator at the top of reactor, gas and water outlet discharge respectively, and mud then settles go back to mud district.
It is by the upflow velocity (6 ~ 12 m/ h) remaining higher that is in operation, and makes granule sludge be in suspended state, also may be used simultaneously
To use higher reactor or to use effluent recycling to obtain high stirring intensity, thus ensure that into water and mud granule
It is fully contacted, promotes organic fast degradation.UASB reactor is provided with special effluent recycling system.UASB reactor is general
For cylindric turriform, feature is to have the biggest ratio of height to diameter, and typically up to 3 ~ 5, the height of process units reactor is up to 15 ~ 20
m.Stable anaerobic reactor uses anaerobic grain sludge, and the sedimentation velocity of mud is more than the rate of climb of sewage.
UASB load-bearing capacity is the biggest, it is adaptable to the high concentrated organic wastewater produced in commercial production, such as wastewater from chemical industry
Process.Compared with other anaerobic biological reactors, the feature of UASB: the highest liquid surface upflow velocity and COD remove negative
Lotus;2. anaerobic sludge grain diameter is relatively big, starts fast, and volumetric loading is high;Reactor anti-shock loading is made plus backflow effect
Ability is strong;3. reactor designs for pyramidal structure, has higher ratio of height to diameter, and floor space is little;4. can be used for SS content high
Process with waste water virose to microorganism;5. UASB reactor has the biggest adaptability to all kinds of waste water, is mainly used in highly concentrated
Degree treatment of Organic Wastewater, energy consumption is low, and sludge output is few.Weak point is to remove the nitrogen in waste water and phosphorus.
3, ICEAS reactor operation principle
ICEAS reactor develops on the basis of sequencing batch active sludge (SBR).Reactor is designed as two along pond length direction
Part, front portion is also referred to as pre-reaction zone for biological selecting area, and rear portion is main reaction region;Rear portion, main reaction region be mounted with liftable from
Move and strain water device;The aeration of main reaction region, precipitation, draining, the Period Process circular flow such as idle;Realize continuum micromeehanics simultaneously,
It is interrupted draining;Eliminate second pond and the sludge recirculation system of conventional activated sludge method;Simultaneously can continuum micromeehanics, be interrupted draining.
In pre-reaction zone, microorganism can be by major part dissolved organic matter, warp in the fast transfer mechanism rapid adsorption sewage of enzyme
Go through the substrate Rapid Accumulation process of a high load capacity.Subsequently in the substrate degradation process of main reaction region one relatively underload of experience.
ICEAS technique integrates reaction, precipitation, draining, function, and the degraded of pollutant is a plug-flow process in time, and micro-
Biology is then among aerobic, anoxia, anaerobism cyclically-varying, thus reaches, to pollutant removal effect, the most also to have relatively
Denitrogenation well, phosphorus removal functional.Especially for industrial wastewater, the volume expanding biological selecting area makes COD and difficult degradation in waste water
Organic pollution carry out sufficient biological hydrolysis reaction wherein.ICEAS reactor major advantage: technological process is simple, accounts for
Ground area is little, invests relatively low;Biochemical reaction motive force is big;Sedimentation effect is good;Flexible operation, strong shock resistance;It is not susceptible to
Sludge bulking;Applied widely, it is suitable for built by separate periods;Surplus sludge volume is little, stable in properties.
The process of the present invention is suitable for the industrial wastewater of the organic properties pollutant containing difficult degradation such as wastewater from chemical industry
Process, in waste water the total removal rate of the organic pollution of COD and difficult degradation be more than 95%, effluent quality can meet in environmental protection
Requirement.
Beneficial effect: the invention have the advantages that 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 (improving Fenton fluid bed IFBR), then carries out
Biochemical treatment (the UASB reactor+ICEAS reactor for treatment of absolute anaerobism), water outlet the most after precipitation, technique composition is reasonable,
Biochemical treatment and materializing strategy the most organically being combined, three main bodys processing unit IFBR, UASB and ICEAS mutually support.
3, commonly industrial wastewater can effectively be processed by the technique that the present invention provides, and can obtain and well process effect
Really, the requirement in environmental protection is met.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.Overcome processing cost high, persistent organic pollutants
Inefficient, 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 content of generation is dirty
Mud 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, ensures effluent quality.Modified model Fenton fluid bed by Fenton oxygen
Change and organically combine with micro-electrolysis reaction, make persistent organic pollutants chain rupture, open loop the most efficiently, resolve into little molecule
Organic substance.Compared with the common Fenton fluid bed of co-content and treating capacity, identical with added pharmaceutical quantities at water inlet indices
In the case of, the clearance of the organic pollution of difficult for biological degradation can be improved 10%, improve the biodegradability of waste water further.
Embodiment 1:
The comprehensive wastewater that certain chemical enterprise produces needs to process, influent concentration COD before treatment≤6000mg/L, pH
6.5~8.5, SS≤300mg/L, NH3-N≤100mg/L, TP≤2.5mg/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.Go out
Water index request COD≤120mg/L, pH 6.5~8.5, SS≤150mg/L, NH3-N≤25mg/L, TP≤1.0mg/L, special
Levy pollutant levels chlorobenzene class≤1.0 mg/L.
Use the group technology in accompanying drawing 1, modified model Fenton fluid bed (IFBR), up-flow anaerobic sludge blanket are used in combination
(UASB) with ICEAS reactor, wastewater from chemical industry is processed;Including regulating reservoir, modified model Fenton fluid bed, degassing neutralization pond,
Coagulative precipitation tank, up-flow anaerobic sludge blanket, ICEAS reactor, be sequentially connected with through water pipe.
This technique includes following operating procedure:
(1) wastewater from chemical industry is after pretreatment, enters regulating reservoir;
(2) it is adjusted rear waste water and is conveyed into modified model Fenton fluid bed by intake pump, by medicine system to modified model Fenton stream
Change in bed and be separately added into H2SO4Solution, FeSO4Solution and H2O2Solution, enters modified model by reflux pump fragrant by part effluent recycling
Pause in fluid bed, in making Fenton fluid bed, present fluidisation state;The oxidizing tower of modified model Fenton fluid bed is cylindrical shape, three pieces of sieve plates
Oxidizing tower is divided into 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 filling out
Material A, ferrum carbon reaction zone is added with filler B;Circulating device is connected to water inlet at exhalant region and oxidizing tower two;By Fenton oxidation district
Fenton's reaction and the micro-electrolysis reaction of ferrum carbon reaction zone, remove part COD and most difficult degradation organic contamination in waste water
Thing;The filler A that Fenton oxidation district is arranged uses quartz sand, and the particle diameter of quartz sand is at 0.5 ~ 1.5 mm;Ferrum carbon reaction zone is arranged
Filler B, uses Alveolate activated carbon, and its honeycomb mouth is consistent with current flow direction;Alveolate activated carbon, wall thickness is 0.5mm, body
Density is 380 ~ 450 kg/m3;First use liquid phase reduction to load zeroth order Nanoscale Iron on the activated carbon, refill and insert the reaction of ferrum carbon
District, refills and inserts ferrum carbon reaction zone;
(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 stirring speed
Degree forms big flco;Entering back into sediment fraction, the big flco of formation realizes precipitate and separate, precipitating sludge warp in settling zone
Sludge treating system processes;
(5) coagulative precipitation tank water outlet enters up-flow anaerobic sludge blanket through infusion, after waste water is entered by reactor lower part, passes upward through
Sludge Bed district, suspended sludge area, three phase separator, then water outlet, biogas is discharged by air chamber;By the effect of anaerobe
Remove part COD and persistent organic pollutants in waste water, reduce the SS of waste water further;Control hydraulic detention time be 12~
36 h;Sludge Bed district granule sludge is tamed by anaerobic sludge;
(6) up-flow anaerobic sludge blanket water outlet enters ICEAS reactor, and reactor is designed as two parts along pond length direction, anterior
Being also referred to as pre-reaction zone for biological selecting area, rear portion is main reaction region;The aeration of main reaction region, precipitation, draining, the process week such as idle
Phase circular flow;Pre-reaction zone arranges micro-aerator, and the water decanter of liftable draining is installed at rear portion, main reaction region;Realize simultaneously
Continuum micromeehanics, is interrupted draining;
(7) discharged wastewater met the national standard after ICEAS reactor for treatment.
Waste water is conveyed into Fenton fluid bed inhalant region through intake pump, by bottom sieve plate water distribution;Waste water enters Fenton stream
Hua Chuan Fenton oxidation district, is separately added into H by medicine system in Fenton fluid bed simultaneously2SO4Solution, FeSO4Solution and H2O2
Solution, is flowed back into the water section in effluent trough in Fenton fluid bed by reflux pump, presents fluidisation in making Fenton fluid bed
State, removes part COD and major part chlorobenzene class organic pollution in waste water by Fenton's reaction;Regulation return flow, controls to fill out
The height that material expands is less than middle sieve plate;Waste water enters ferrum carbon reaction zone through middle sieve plate, in iron-carbon micro-electrolysis condition
Under, persistent organic pollutants in catalysis oxidized waste water;The waste water aoxidized through iron-carbon micro-electrolysis catalysis passes through upper strata sieve plate, through going out
Mill weir enters in effluent trough, enters next processing unit by outlet pipe;Top effluent trough connects circulating device, divides two and enter
Water pipe is respectively fed to water inlet at the two of bottom, Fenton oxidation district and bottom, ferrum carbon reaction zone, flows back into discharge and is respectively Q1With
Q2, Q1With Q2With m3/ d meter ratio is 8:1.During Fenton fluidized bed processing, H2O2It is 2.5:1 with concentration ratio (mg/L) of COD,
H2O2With Fe2+Mol ratio be 4:1, the waste water mean residence time in Fenton oxidation district controlled at 1 hour, and waste water is at ferrum carbon
The mean residence time of reaction zone controls at 30 minutes, regulates waste water in Fenton fluid bed by medicine system and online pH meter
PH value, makes pH value maintain between 3.0~4.0.
The oxidizing tower ratio of height to diameter of up-flow anaerobic sludge blanket is 4, and maintenance upflow velocity 9 m/h that is in operation makes granule dirty
Mud is in suspended state;Design volumetric loading is 11kgCOD/(m3D).
ICEAS reactor, the aeration of its main reaction region, precipitation, draining, the process cycle period such as idle are 4 hours, expose
Gas, precipitation, draining, the distribution of idle time are respectively 120 minutes, 60 minutes, 40 minutes, 20 minutes;Reactor runs mud
Load is 0.3 kgCOD/(kgMLSS d).
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 sees below
Table.
Table 1 leading indicator each unit treatment effect catalog