CN109052748A - A kind of advanced treatment process of coking wastewater - Google Patents
A kind of advanced treatment process of coking wastewater Download PDFInfo
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Abstract
The invention discloses a kind of advanced treatment process of coking wastewater, comprise the steps of: (1) being water inlet with the coking wastewater Jing Guo biochemical treatment, carry out iron-carbon micro-electrolysis reaction；(2) the coking wastewater after iron-carbon micro-electrolysis reaction completes the advanced treating of coking wastewater using coagulation, precipitating.The advanced treatment process treated water outlet CODcr≤80mg/L, stably reach the in line standard of " coking chemistry emission of industrial pollutants standard " (GB16171-2012).The technique is without consuming electric power resource or only consuming a small amount of electric power resource, and easy to operate, integrated operation expense is low.
Description
Technical field
The present invention relates to a kind of advanced treatment process of coking wastewater, belong to technical field of sewage.
Background technique
Coking wastewater is the waste water generated in coal coke, gas purification and coke chemicals removal process, difficult containing high concentration
The pollutants such as degradation CODcr (COD), ammonia nitrogen, volatile phenol, cyanide.By raw coal property, ammonia still process production technology and coke
Change the influence of the factors such as Product recycling, the coking wastewater ingredient of generation is extremely complex, and water quality and water fluctuate very big, mesh
Before be still one of high-leveled and difficult waste water, if coking wastewater be unable to stably reaching standard discharge, natural environment will be polluted, and lead to ecology
Environmental disruption.
Due to the network minimal of biochemical treatment, so in practical applications, a large amount of sewage can only first pass through biochemical treatment
To reduce pollutant index.If the index after biochemical treatment can't be up to standard, need to carry out advanced treating.Coking wastewater is usual
Using pretreatment+biochemistry+advanced treating process route, mesophytization section generallys use work based on conventional activated sludge process
Skill, such as AAO (anaerobic- anoxic- oxic), OAO (aerobic-anoxia-aerobic), AOAO (anerobic-aerobic-anerobic-is aerobic), the work
Skill is undesirable to the removal effect of CODcr and ammonia nitrogen, it is difficult to make to be discharged qualified discharge.
The coking waste water treatment process of domestic and international iron and steel enterprise is still to be aided with corresponding using biochemical method as leading technology at present
Further treatment technique.The further treatment technique that Treatment of Coking Effluent uses at present, specifically include that coagulant sedimentation, absorption method,
Biochemical process, advanced oxidation processes and membrane separation process.Coking wastewater mainstream further treatment technique situation is as follows:
(1) absorption method and coagulant sedimentation are at present using more coking wastewater deep treatment technology, following research
Direction is exploitation coagulant and adsorbent efficient, highly selective, without secondary pollution.Presently, there are deficiency be stability up to standard
Difference, pollutants removal rate is lower, needs to further decrease processing cost and improves treatment effect.
(2) MBR method (membrane bioreactor) and membrane separation process have many advantages, such as that treatment effeciency is high, occupied area is small, recently
Certain application at home and abroad has been obtained in coking wastewater deep treatment within several years, future will be coking wastewater deep treatment field
Key technology.Main direction of studying for MBR method and membrane separation process is to develop the filter membrane of high efficiency, low cost, needs to solve to drop
Low investment is at high cost and the high problem of late maintenance cost.
(3) advanced oxidation processes have many advantages, such as that treatment effeciency is high, oxidation rate is fast, without secondary pollution, useless in coking at present
Water depth process field using more.From the point of view of current applicable cases, it is more to be primarily present control node, and operation requires
The deficiencies of height and high operating cost, needs developing low-cost, efficient oxidant and catalytic activity is good, stability is strong, effect
The high catalyst of rate.
(4) research in the combined treatment process of process above method and coking wastewater deep treatment field and application side
To.Treatment effect and stability are substantially better than single technique, but there are many process flow, to the professional ability of operator require compared with
Height, management cost are relatively high.
105948338 A of CN discloses a kind of advanced treatment method for carbonization wastewater and system.The deep treatment method be
Excessive process flow, including microwave radiation-iron-carbon micro-electrolysis-Fenton-coagulation-precipitating-micro-filtration step are provided with after biochemical treatment
Suddenly, cost is very high, and adds active carbon as adsorbent in coagulation, needs to regenerate or replace, will form secondary pollution.
With increasingly strict, the industry of high energy consumption low output poor benefit of global environmental protection standard, being badly in need of exploitation can be in stabilization
The technology of low operating cost under the premise of up to standard, coking industry are particularly true.
Constantly there are new advanced treatment method for carbonization wastewater and technology to be born in recent years, but still can not solve to stablize simultaneously
Water outlet, problem easy to operate, operating cost is low.
Although coking wastewater processing method also gradual perfection, stable water outlet is still poor in actual production, and transports
Costly row is still enterprise's pain, and treatment facility is caused not play maximum effect, existing technology of root itself
Defect problem, there is also the reason of management and economic aspect to limit.It is increasingly strict with China's sewage drainage standard, enterprise
Environmental liability is also increasingly heavier, and the water total amount and recycling rate of waterused of coke-oven plant have a long way to go compared with advanced country.
Summary of the invention
Present invention solves the technical problem that being, the process of advanced treatment of wastewater is longer, higher cost, and wastewater treatment efficiency is not
Good, effluent quality is unstable.
The technical scheme is that a kind of advanced treatment process of coking wastewater is provided, by being formed with following step:
(1) it is water inlet with the coking wastewater Jing Guo biochemical treatment, carries out iron-carbon micro-electrolysis reaction；
(2) the coking wastewater after iron-carbon micro-electrolysis reaction completes the depth of coking wastewater using coagulation, precipitating
Reason.
The present invention also provides a kind of advanced treatment process of coking wastewater, comprise the steps of:
(1) coking wastewater is first pre-processed, then carries out biochemical treatment；Coking wastewater after biochemical treatment is subjected to iron
Carbon micro-electrolysis reaction；
(2) the coking wastewater after iron-carbon micro-electrolysis reaction completes the depth of coking wastewater using coagulation, precipitating
Reason.
Advanced treatment process of the invention has main steps that: pretreatment-biochemical treatment-iron-carbon micro-electrolysis-coagulation-is heavy
It forms sediment.Wherein only consider that advanced treatment process section, the technique are that iron-carbon micro-electrolysis-coagulation-is only carried out after existing biochemical treatment
Three steps are precipitated, advanced treating can be completed.For more specifically, advanced treatment process of the invention is i.e. by above-mentioned steps group
At.
Unlike other advanced treatment process, the present invention only needs iron-carbon micro-electrolysis-step of coagulation-precipitating three i.e.
The stably reaching standard of effluent quality can be achieved, and avoid excessive process flow.The unexpected technology effect of of the invention one
Fruit is: can use very low process costs and reaches and other techniques quite even preferably treatment effect.
Preferably, iron-carbon micro-electrolysis reaction is carried out in iron-carbon micro-electrolysis reactor；Institute's iron-carbon micro-electrolysis reactor is under
It is supreme successively are as follows: water distributing area, filler reaction zone and clear water zone, iron-carbon micro-electrolysis filler are located in filler reaction zone, filler reaction
Hydraulic detention time in area is 45-60min.
Preferably, the height of the water distributing area is 1.2-1.5m.
Preferably, the height of the clear water zone is 0.3-0.5m.
Preferably, the iron content in the filler reaction zone in iron-carbon micro-electrolysis filler is 55-60% (mass percent).
Iron-carbon micro-electrolysis filler is made of iron, carbon and a small amount of binder.Wherein, binder is used to filler bonding balling-up, and dosage is less,
Iron content formula rate is 55-60%, and balling-up partial size is 8-12mm, does not increase clay as binder, bulk density 1.2-
1.4t/m3。
The present invention is surprised to find that the treatment effect (especially COD index) of the height coking wastewater of iron content has significantly
It influences, preferably iron content is 55-60%.
Preferably, the bulk density of iron-carbon micro-electrolysis filler is 1.2-1.4t/m in the filler reaction zone3。
Preferably, the partial size of iron-carbon micro-electrolysis filler is 8-12mm in the filler reaction zone.Filler diameter can according into
Aqueous suspension adjustment.
Preferably, it is equipped with sparge pipe in water distributing area bottom, water inlet enters water distributing area by sparge pipe, then flows sequentially through filler
Reaction zone, clear water zone, then sequentially enter coagulating basin and sedimentation basin.
Preferably, when treating capacity is smaller, iron-carbon micro-electrolysis reactor, coagulating basin and sedimentation basin are integrated.Processing
When measuring larger, the structural shape with divergence type is needed.
Microelectrolysis processing waste water has just caused the concern of environmentally friendly researcher both at home and abroad since birth, and has carried out a large amount of
Research, have many patents and practical technique achievement.Currently, micro electrolysis tech is quickly grown in field of industrial waste water treatment,
It has been used to print and dye, be electroplated, petrochemical industry, pharmacy, gas washing, industrial wastewaters such as printed circuit board production and containing arsenic, fluorine-containing
The processing engineering of waste water, and have received good economic benefit and environment protecting.Weak electrolysis mechanism has well the decoloration of waste water
The effect of processing, and the treatment of wastes with processes of wastes against one another, operating cost is low, therefore will have good prospects for commercial application in China.
Iron-carbon micro-electrolysis technology is one kind of micro electrolysis tech.Using Principles of Metal Erosion method, primary battery is formed to waste water
The good process handled, also known as internal electrolysis, Filtration with Iron Filings etc..Micro electrolysis tech is current processing high concentration organic waste
A kind of ideal technology of water, also known as internal electrolysis.It is to utilize the light electrolysis material being filled in waste water in cold situation
Expect that itself generating 1.2V potential difference carries out electrolysis processing to waste water, to achieve the purpose that degradable organic pollutant.
The processing of iron-carbon micro-electrolysis big, high toxicity, high chroma, difficult biochemical waste water for organic concentration, can be significantly
The coloration and COD of waste water are reduced, improving B/C ratio (BOD/CODcr, BOD, that is, biochemical oxygen demand (BOD)) value is the biochemical of raising waste water
Property.
Iron-carbon micro-electrolysis technology has a small amount of application in coking wastewater industry, but is mainly used in the pretreatment of front end at present,
Temporarily do not find there is successful application case in the advanced treating of end in industrial applications.
Process of the invention includes: three reactor, coagulating basin, sedimentation basin technique units.Coking wastewater is by life
After change processing, into Fe-C micro electrolysis reactor, iron-carbon micro-electrolysis filler is placed in reactor, is existed using iron and carbon
The very poor formation primary battery of current potential in solution, makes the cyclic organic materials such as macromolecule organic or aromatic hydrocarbon open loop chain rupture in waste water,
Heavy metal complex can be abolished simultaneously, and there is destruction etc. to conjugation chromophoric group, so that waste water is handled, this
Outside, after the iron ion release in iron-carbon filling material, the molysite with cohesion function, the appropriate dosing coagulant in coagulating basin be will form
And flocculant, after waterpower or mechanical stirring, into carrying out mud-water separation, clear water outlet or reuse in sedimentation basin.
Fe-C micro electrolysis reactor includes sparge pipe, water distributing area, filler reaction zone, clear water zone, catch basin.Utilize big resistance
Water distribution, water distributing area height 1.2-1.5m, filler reaction zone hydraulic detention time 45-60min, clear water zone height 0.3-0.5m, collection
Sink uses finger-type weir or ring dam.Two-stage water distribution reduces dead angle；Steam joint back washing device is passed through using Automatic Control
Resistance is detected, runing time is cooperated, realizes and automatically controls, reduces labor intensity, while reducing human factor to operating parameter control
The influence of system.
Compared with prior art, the beneficial effects of the present invention are:
1. the advanced treatment process of alternative original long process has and significantly saves labour turnover, reduces running cost
Potentiality.
It is discharged CODcr 2. treated, stably reaches " coking chemistry emission of industrial pollutants standard " (GB16171-
2012) in line standard, i.e. CODcr≤80mg/L.
3. Fe-C micro electrolysis reactor does not block, stability is good, stable effluent quality；
4. it is easy to operate without consuming electric power resource, power consumption is reduced, maintenance of electric device cost, comprehensive fortune are reduced
Row expense is low；
5. running node is few, human factor influences technique few；No strong corrosive medicament is added, and operational safety is high；
6. it is low to site requirements, it is transformed using existing facility；
7. being applicable in broad spectrum activity, there is stronger Combined Treatment ability to high-concentration hardly-degradable waste water.
Detailed description of the invention
Fig. 1 shows the prior art flow charts of the sewage treatment plant.
Fig. 2 indicates the process flow chart of the application.
The process flow chart of Fig. 3 expression comparative example.
The process flow chart of Fig. 4 expression comparative example.
Specific embodiment
Below with reference to embodiment, the invention will be further described.
(1) project briefing
The coking production workshop of Hunan steel plant mainly produces coke, crude benzol, coal tar, sulfate of ammoniac etc., produces coke per year
Scale is 2,300,000 tons, and waste water yield is 100m3/ h, the wastewater flow rate that unit coke generates is about 0.375m3/ ton is burnt.Production is burnt
Carbon is carried out in certain temperature range, in order to save production cost, reduces the use of extra power medium, coke is produced
It lowers as far as possible, with into water saving measures are taken, to save a large amount of production cost.After plant manufacturing process changes, make to give up
Water yield is by original 100m3/ h drops to 70m3/ h, ton coke waste water reduced quantity is by 0.375m3/ ton coke drops to 0.263m3/
Ton is burnt, but brings adverse effect therewith, i.e. not increased by the hard-degraded substance of Pintsch process in the waste water of workshop discharge, at
Point more complicated, bio-toxicity is stronger, and pollutant concentration increases, and color is color of soy sauce, causes matched sewage treatment plant of the factory
Bio-chemical effluent index is higher compared to the index of similar waste water, and advanced treating process is partially long, and overall operation expense is excessively high.
Prior art:The Designing Sewage Treatment Plant scale is 2400m3/d(100m3/ h), execute " coking chemistry industrial pollution
Object discharge standard " (GB16171-2012) in line standard.Using the overall craft of " pretreatment+biochemical treatment+advanced treating ",
Concrete technology flow process is as shown in Figure 1.Wherein: including 2# conditioning tank and before, biochemical treatment includes level-one AO and second level for pretreatment
AO, advanced treating include level-one Fenton and technique later.
(2) process description
1. pretreatment: including oil separator, 1# conditioning tank, air bearing, 2# conditioning tank and accident pool.
After waste water is collected in workshop, pumped to oil separator, under the effect of gravity, light oil is bubbled through the water column, and heavy oil is sunken to pond
Bottom excludes oil slick and greasy filth by the Skimming oil and Scraping sediment Machine.1# conditioning tank homogeneous average is flowed into again, is then promoted to airfloat equipment, is thrown
Add aluminium polychloride (PAC) and polyacrylamide (PAM), sticks the oils in removal sewage using a large amount of fine gas bubbles of generation
And impurity, it realizes and is separated by solid-liquid separation, clear liquid flows into 2# conditioning tank, Balance Water Quality water.Accident pool is mainly used to receive workshop exception
Draining and excess draining.
2. biochemical treatment: including level-one AO and second level AO
Under the action of anoxic microorganism and aerobic microbiological, the organic pollutant in sewage is decomposed under aerobic state
H20、、CO2And heat, organic nitrogen issue unboiled water solution ammonification in anaerobic condition and first generate inorganic nitrogen, issue caliche in aerobic state
Effect generates nitrate nitrogen, is then back to anoxic pond and is converted into N2It is dispersed into air, to realize denitrogenation.
Level-one AO and second level AO series operation, when sewage is after level-one AO processing, organic matter is degraded major part, enters
The coking wastewater of second level AO usually lacks low molecule carbon source, to realize that denitrogenation needs to add the additional carbons such as glucose, and should be to
Aerobic tank supplements lye to maintain suitable pH environment needed for microbe survival.
3. advanced treating: including level-one Fenton, second level Fenton, BAF, photocatalytic oxidation pool, the pond MBBR, sand filtration etc..
Biochemical treatment is discharged, the inflow pond level-one Fenton, after conditioning tank pH 3-4, adds ferrous sulfate, hydrogen peroxide carries out
Reaction, the hydroxyl radical free radical (OH) of generation, using its superpower oxidisability, the organic matter of oxygenolysis sewage, reaction is completed
After add lye readjustment pH7-8, then add PAC and PAM flocculation sedimentation and be separated by solid-liquid separation.Supernatant enters second level Fenton,
Oxygenolysis is carried out again.
Second level Fenton supernatant enters biological aerated filter (BAF), under the action of aerobic and facultative microbe, degradation
Pollutant after Fenton open loop chain rupture, BAF water outlet is passed through ozone from photocatalytic oxidation pool is flowed into, in catalyst and ultraviolet
Further open loop and decomposing pollutant under the action of light.Photocatalytic oxidation pool water outlet flows into the pond MBBR, in the work of aerobic microbiological
With lower continuation degradable organic pollutant.
Sewage after processing is promoted to sandfiltration pot again and is filtered, clear water outlet or reuse.
(3) Inlet and outlet water index
| Raw water | Pretreatment water outlet | Biochemical treatment water outlet | Advanced treating water outlet | Discharge standard | |
| CODcr | 4500-5500 | 4500-5300 | 350-400 | 65-75 | 80 |
| SS | 200-400 | 150-300 | 300-500 | 20-30 | 50 |
| NH3-N | 60-150 | 60-140 | 0-12 | 1.0-6.0 | 10 |
| TN | 300-400 | 240-350 | 25-40 | 10-15 | 20 |
| TP | 2.0-5.0 | 1.0-3.0 | 0.4-2.0 | 0.1-0.2 | 1.0 |
| Cyanide | 25-40 | 24-38 | 0.1-0.15 | 0.12-0.18 | 0.2 |
| Volatile phenol | 700-850 | 700-800 | 0.06-0.17 | 0.1-0.2 | 0.3 |
Note: the unit in upper table is mg/L.COD refers both to CODcr, and unit is also mg/L, similarly hereinafter.
(4) main units specification and load meter
(4) conclusion
The implementation of the technique can make water outlet reach " coking chemistry emission of industrial pollutants standard " (GB16171-2012)
In line standard, i.e. CODcr≤80mg/L.But process flow is very long, and complicated for operation, operating cost is very high.
Embodiment (iron-carbon micro-electrolysis):
(1) project briefing
The water outlet that water sample is above-mentioned second level AO is tested, advanced treating is carried out to waste water using the method for the micro- solution of iron charcoal.
Fe-C micro electrolysis reactor, diameter 300mm are highly 1150mm, and lower part 150mm is water and air distributing area, installation
Iron-carbon filling material is filled on partition and aerator, top.The bottom of from up along longitudinal direction highly in 460mm, 640mm, 820mm and 1000mm
Place's setting water outlet, when inflow is 50L/h, the corresponding reaction time is 30min, 60min, 90min, 120min.
Iron carbon filler needed for iron-carbon micro-electrolysis mainly includes Fe, C and a small amount of adhesive, is contained by the mass percent of Fe
Amount is to distinguish classification.
Using identical test method, to iron content be respectively 50%, 55%, 60%, 65% four kinds of iron carbon fillers into
Row comparative test.
Carry out Fe-C micro electrolysis experiment.
(2) process description (Fig. 2)
Iron carbon ball filler is fitted into reactor first, opens aeration, aeration quantity 30L/min；Sewage adds sulfuric acid, by pH
It is adjusted to 4 or so；Start to intake by the sewage quantity of 50L/H；Respectively when the reaction time is 30min, 60min, 90min, 120min
It samples and observes；After adding PAM stirring precipitating, water sample chemical examination is carried out.
(3) Inlet and outlet water index
1. first group: iron content is the detection data of 50% (mass percent, similarly hereinafter)
2. second group: the detection data that iron content is 55%
3. third group: the detection data that iron content is 60%
4. the 4th group: the detection data that iron content is 65%
(4) conclusion
1. first group, the 4th group of reaction time tend towards stability substantially in 60min~90min, COD removal rate 55.1%
Between~59.3%, CODcr is discharged in 150mg/L or so；When iron content be 50% when, water outlet color be it is yellowish, work as iron content
When being 65%, water outlet color is milky.
2. second group, reaction time of third group tend towards stability substantially in 60min, COD removal rate 81.8%~
Between 88.2%, CODcr is discharged in 43.2-67.4mg/L or so；When iron content is 55%, water outlet color is colorless clear,
When iron content is 60%, water outlet color is colorless clear；
3. Macro or mass analysis, Fe-C micro electrolysis technique has good treatment effect to coking COD of sewage cr, coloration, smell；Instead
Answer pH value control between 3-4, for the investment on control engineer application, reaction time control is compared between 45min~60min
Properly.
Comparative example 1:(coagulating sedimentation)
(1) project briefing
The water outlet that water sample is above-mentioned second level AO is tested, advanced treating is carried out to waste water using the method for coagulation.
(2) process description (Fig. 3)
Water sampling (secondary clarifier effluent after biochemical treatment) 1L is put into 1000ml beaker, totally 8 experiment water samples, is added
PAC, dosage are respectively 100mg, 200mg, 300mg, 400mg, 500mg, 600mg, 700mg and 800mg, are continuously stirred
After 2min, reaction 30min is stood, the supernatant after observation clarification, discovery is in rising trend with the increase of dosage, but
Supernatant transparent lightness is begun to decline when 400mg.
According to the above results, choosing PAC dosage is 300mg, 320mg, 340mg, 360mg, 380mg and 400mg, is used
The above method is tested again, and test optimum dosage is 320mg, and supernatant effect is compared to poor when dose decreases or increases.
The test of next step determines the dosage of PAM based on PAC dosage 320mg.According to the preliminary trial throw of PAM
As a result, can initial setting dosage be 5mg, 10mg, 15mg, 20mg, 25mg, 30mg, 35mg and 40mg, water sampling 1L, totally 8
It is a, after respectively adding PAC320mg, after continuously stirring 2min, is successively added by the amount of above-mentioned PAM, continuously stir 5min, it is quiet
Silent 30min detects COD result between 280-320mg/L, and effect is best when wherein PAM is 30mg dosage.
Comparative example 2:(Fenton)
(1) project briefing
The water outlet that water sample is above-mentioned second level AO is tested, advanced treating is carried out to waste water using the method for Fenton.
(2) process description (Fig. 4)
Water sampling (secondary clarifier effluent after biochemical treatment) 1L is put into 1000ml beaker；H is added2SO4Adjust wastewater pH to
3.5；FeSO is added4, stir evenly；H is added2O2, after continuously stirring, then stand 5~60min of reaction；Be added NaOH adjust pH to
7.5；After PAM is added, 30min is stood；CODcr is surveyed in sampling.
By consulting related literatures, and COD:H is obtained through preliminary test2O2Molar ratio be 1:4 when be more satisfactory
Add ratio, COD mole press O2Molecular weight calculates.With this condition, by adding the Fe of different proportion2+Carry out Analysis for CO D to go
Except the changing rule of rate.
11 1L experiment water samples are taken, are separately added into sulphur acid for adjusting pH to 3.5, according to COD:H2O2:FeSO4Molar ratio is 1:
4:1,1:4:1.5,1:4:2,1:4:2.5,1:4:3,1:4:3.5,1:4:4,1:4:4.5,1:4:5,1:4:5.5 and 1:4:6 are thrown
Add FeSO4, dosage correspond to 6.8ml, 10.2ml, 15.2ml, 17.0ml, 20.4ml, 23.8ml, 27.2ml, 30.6ml,
H is added in 34.0ml, 37.5ml and 40.9ml, after mixing evenly, each water sample moderate2O2For 5.1ml, continuously stir after 30min again
Reaction 30min is stood, pH to 7.5 is then adjusted back.
By detecting the COD index of 11 water samples, in H2O2Under conditions of dosage is constant, with FeSO4The increase of dosage,
Fe2+Within the scope of 1~2.5mol, COD removal rate is gradually increased, then decline, minimized in 3.5mol, then again on
It rises, declines again in 4.5mol, " M " shape is presented in COD removal rate change curve.According to empirical curve it can be concluded that, COD:
H2O2:FeSO4Molar ratio can obtain optimal COD removal rate at 1:4:2.5~3 and 1:4:4~4.5 section.
A reasonable reaction time is needed on engineer application, avoids medicament reaction insufficient, causes water outlet COD unstable
It is fixed, while the indefinite extension reaction time also should be avoided, cause reaction Pool body design excessive and the investment waste of generation, therefore, if
A reasonable reaction time is needed on meter.By detecting the COD index of 11 water samples, COD:H is obtained2O2:FeSO4Molar ratio
Therefore obtaining optimal COD removal rate in 1:4:2.5~3 and the section 1:4:4~4.5 selects molar ratio for 1:4:2.5 and 1:
Dispensing ratio of the 4:4.5 as test is divided into COD removal rate variation feelings of the two group analysis comparison under differential responses time conditions
Condition.
There are two reaction time variables, i.e. mixing time and time of repose.Two different dispensing molar ratio experimental groups, then
It is divided into the comparative analysis of the different reaction time progress COD removal rate of two batches with time of repose according to mixing time.
First group, under the conditions of setting molar ratio as 1:4:2.5, compare different mixings time and different time of repose pair
The influence of COD removal rate.First water sample uses mixing time for 30min, and time of repose is sampled from 5~60min every 5min
Analysis；Second batch water sample uses mixing time for 15~60min, and time of repose takes 30min, every 5min sampling analysis.
Second group, under the conditions of setting molar ratio as 1:4:4.5, compare different mixings time and different time of repose pair
The influence of COD removal rate.First water sample uses mixing time for 30min, and time of repose is sampled from 5~60min every 5min
Analysis；Second batch water sample uses mixing time for 15~60min, and time of repose takes 30min, every 5min sampling analysis.
First group and second group of test result are as it can be seen that COD:H2O2:FeSO4Molar ratio 1:4:2.5's or 1:4:4.5
Under the conditions of, COD removal rate curve is essentially identical, and the reaction time is positively correlated with COD removal rate.Wherein, being stirred to react the time exists
Start to tend towards stability when 25min or so, effect is best when 30min, is further added by the reaction time and COD removal rate is not further added by；It is quiet
Set the reaction time starts to tend towards stability in 20min, and effect is best when 30min, is further added by the time and COD removal rate no longer increases
Add.
(3) conclusion
By being tested using secondary clarifier effluent of the Fenton reagent processing coking wastewater after biochemical, show: Fenton medicine
Agent is added than being " M " type with the invariance curve of COD removal rate, and highest removal rate is up to 84%；Medicament, which most preferably adds molar ratio, to be had
Two sections, i.e. COD:H2O2:FeSO4=1:4:2.5~3 and the section 1:4:4~4.5, should avoid the undesirable 1:4:3 of effect
~4；Consider from Technological Economy angle, optimum reacting time can use 30~45min；Control Fenton adding of agent ratio and reaction
Time can make water outlet COD be reduced to 80-100mg/L.
Comparative result table:
As a comparison, the above method and MBR method analyze the applicable cases of such Sewage advanced treatment, specific work
Skill and result are as follows:
Remarks: above-mentioned medicament unit price, 50%H2SO4: 500 yuan/t, 23.5%FeSO4: 200 yuan/t, 27.5%H2O2:1150
Member/t, 99%NaOH:3000 member/t, 28%PAC:1800 member/t, 12,000,000 PAM:12800 members/t, Fe-C micro electrolysis filler:
10000 yuan/t；MBR film, flux press 10L/m2H and film unit price press 200 yuan/m2It calculates；3000 yuan/t of bentonite, active carbon 8000
Member/t, 9000 yuan/t of resin.
Claims (10)
1. a kind of advanced treatment process of coking wastewater, which is characterized in that comprise the steps of:
(1) it is water inlet with the coking wastewater Jing Guo biochemical treatment, carries out iron-carbon micro-electrolysis reaction；
(2) the coking wastewater after iron-carbon micro-electrolysis reaction completes the advanced treating of coking wastewater using coagulation, precipitating.
2. a kind of advanced treatment process of coking wastewater, which is characterized in that comprise the steps of:
(1) coking wastewater is first pre-processed, then carries out biochemical treatment；It is micro- that coking wastewater after biochemical treatment is subjected to iron carbon
Cell reaction；
(2) the coking wastewater after iron-carbon micro-electrolysis reaction completes the advanced treating of coking wastewater using coagulation, precipitating.
3. advanced treatment process as claimed in claim 1 or 2, which is characterized in that carry out iron in iron-carbon micro-electrolysis reactor
Carbon micro-electrolysis reaction；Institute's iron-carbon micro-electrolysis reactor is from the bottom to top successively are as follows: water distributing area, filler reaction zone and clear water zone, iron carbon
Micro-electrolysis stuffing is located in filler reaction zone, and the hydraulic detention time in filler reaction zone is 45-60min.
4. advanced treatment process as claimed in claim 3, which is characterized in that the height of the water distributing area is 1.2-1.5m.
5. advanced treatment process as claimed in claim 3, which is characterized in that the height of the clear water zone is 0.3-0.5m.
6. advanced treatment process as claimed in claim 3, which is characterized in that iron-carbon micro-electrolysis filler in the filler reaction zone
In iron content be 55-60%.
7. advanced treatment process as claimed in claim 3, which is characterized in that iron-carbon micro-electrolysis filler in the filler reaction zone
Bulk density be 1.2-1.4t/m3。
8. advanced treatment process as claimed in claim 3, which is characterized in that iron-carbon micro-electrolysis filler in the filler reaction zone
Partial size be 8-12mm.
9. advanced treatment process as claimed in claim 3, which is characterized in that water distributing area bottom be equipped with sparge pipe, water inlet by
Sparge pipe enters water distributing area, then flows sequentially through filler reaction zone, clear water zone, then sequentially enter coagulating basin and sedimentation basin.
10. advanced treatment process as claimed in claim 9, which is characterized in that iron-carbon micro-electrolysis reactor, coagulating basin and precipitating
Pond is integrated.
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