CN102372401A - Iron-carbon micro-electrolysis-dynamic membrane wastewater deep treatment process - Google Patents

Iron-carbon micro-electrolysis-dynamic membrane wastewater deep treatment process Download PDF

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CN102372401A
CN102372401A CN2011102946495A CN201110294649A CN102372401A CN 102372401 A CN102372401 A CN 102372401A CN 2011102946495 A CN2011102946495 A CN 2011102946495A CN 201110294649 A CN201110294649 A CN 201110294649A CN 102372401 A CN102372401 A CN 102372401A
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wastewater
iron
dynamic
electrolysis
film component
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CN102372401B (en
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张亚雷
褚华强
潘碌亭
周雪飞
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Tongji University
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Tongji University
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Abstract

The invention relates to an iron-carbon micro-electrolysis-dynamic membrane wastewater deep treatment process. The process comprises the following steps: pretreating pollutants in industrial wastewater by iron-carbon micro-electrolysis so as to remove partial pollutants and improve the biochemical performance of the wastewater; then, carrying out microorganism degradation by mainly using mixed liquids in a hydrolysis acidification pool and an aerobic dynamic membrane reaction pool so as to remove the pollutants; and finally, completing the solid-liquid separation and water discharge process of the mixed liquid with a dynamic membrane assembly. The invention aims at providing the iron-carbon micro-electrolysis-dynamic membrane wastewater deep treatment process which is simple in process flow and efficient; the process can be effectively used for removing the difficultly-degradable organic substances in the industrial wastewater and improving the biochemical performance of the wastewater, and has obvious decoloring effect and good solid-liquid separation effect; the effluent is clear and does not contain suspended particles; and the process is suitable for standard-reaching discharge and deep treatment of various industrial wastewaters (such as dyeing and printing wastewater, pharmaceutical wastewater, heavy metal wastewater, coking wastewater, paper-making wastewater and the like), and the index of the quality of the treated effluent can meet the water quality standard of reused water.

Description

The waste water advanced treatment process of the little electrolysis-Dynamic Membrane of iron charcoal
Technical field
The invention belongs to technical fields such as industrial wastewater pollution thing degraded removal and advanced treatment and reclamation, be specifically related to the little electrolysis of a kind of iron charcoal-Dynamic Membrane advanced treatment of industrial waste water technology.
Background technology
According to the whole nation source of pollution generaI investigation of accomplishing in 2010 first time, 738.33 hundred million tons of China's trade effluent contracts amounts, 236.73 hundred million tons of quantity dischargeds, waste water year 458.52 hundred million tons of treatment capacities.Principal pollutant generation in the trade effluent: 3145.35 ten thousand tons of CODs, 201.67 ten thousand tons of ammonia nitrogens, 54.15 ten thousand tons of petroleum-type, 12.38 ten thousand tons of volatile phenols, 2.43 ten thousand tons in heavy metal.China's water resources shortage, the advanced treatment of industrial waste water reuse becomes numerous geographic selections as a feasible program of conserve water resource.Because the complicacy and the bio-refractory property of trade effluent component, the efficient advanced treatment of industrial waste water technology that can select for use now seldom.Different sorts gets trade effluent; Like paper waste, dyeing waste water, pharmacy waste water, coking chemical waste water, heavy metal wastewater thereby etc., after various biochemistry combination process processing, effluent quality generally exists: COD200-300mg/L; Colourity 100-400 degree; B/C is than < 0.2, biodegradability is relatively poor, is difficult to reach the emission standard of regulation in " integrated wastewater discharge standard ".To the situation that present environmental protection pressure increases day by day, sewage drainage standard will be strict day by day.
Little electrolysis is called interior electrolysis, zeroth order iron processes etc. again.Little electrolysis process mainly is to utilize the chemical reaction between iron and the carbon and the correlated response that causes comes waste water is handled.Because it has unique degradation effect to hard-degraded substance; Can improve the biodegradability of waste water; Often as the preconditioning technique of waste water, along with the further investigation to little electrolysis working mechanism, little electrolysis is no longer as a kind of single technology; And with the other technologies coupling, improve the treatment effect of subsequent technique through little electrolytic pre-treatment.Little electrolysis as the advanced treatment technology mainly is after secondary biochemical treatment; The material of biodegradability degraded fully basically in the waste water, remaining is hard-degraded substance, utilizes little electrolytic mechanism; Further improve the removal effect of organic pollutant, make its water outlet can qualified discharge.
But the subject matter that little electrolysis exists in actual motion be the iron filings treatment unit after the operation of for some time, filling surface forms passive film, iron filings are prone to caking, phenomenons such as channel occur, reduce treatment effect greatly; Little electrolysis treatment waste water normally carries out under acidic conditions, causes the stripping quantity of iron big, adds sedimentable matters a large amount of with generation in the alkali simultaneously.Therefore, control effectively that harden in the iron-carbon filling material surface, passivation, and in the control filler iron ion to separate out this The Application of Technology crucial.
Dynamic membrane is a kind of new separation technology of rising in recent years, utilizes to add that PM for particulate matter plays the solid-liquid separation effect at the filter cake that the macropore supporting body surface forms in precoating paint or the mixed solution to be filtered.The dynamic film component inexpensive has good solid-liquid separation efficiency (water outlet does not contain suspended substance basically), and filtration flux is big, and the film pollution is easy to control, and back flushing and flux recover easily.Utilization adds powder can further improve filter effect, further improves effluent quality.
Summary of the invention
The object of the present invention is to provide a kind of technical process simply, the little electrolysis of iron charcoal efficiently-Dynamic Membrane advanced treatment of industrial waste water technology, this technology can effectively be removed hardly degraded organic substance in the trade effluent, improves wastewater biodegradability; Decolorizing effect is remarkable; Good effect of separating solid from liquid, water outlet is limpid, does not contain suspended particulate; Be applicable to the qualified discharge and the advanced treatment of various trade effluents (like dyeing waste water, pharmacy waste water, heavy metal wastewater thereby, coking chemical waste water, paper waste etc.); Handle back water outlet CODcr < 50 mg/>L; < 15 times, other water-quality guideline all can satisfy middle water reuse water quality standard to colourity.
The present invention at first adopts the little electrolysis of iron charcoal that pollutent in the trade effluent is carried out pre-treatment, removes the part pollutent and improves the biodegradability of waste water; Afterwards, pollutent is mainly removed by mixed solution microbiological deterioration in hydrolysis acidification pool and the aerobic Dynamic Membrane reaction tank; Finally, mixed solution solid-liquid separation exiting water process is accomplished by dynamic film component.In the Dynamic Membrane reaction tank Pollutant Treatment process; Can according to circumstances add PM for particulate matters such as zeyssatite, zeolite; Improve microbial species group structure in the mixed solution, improve pollutant removal, and can improve dynamic membrane filtering flux, prolongation filtration time, effectively controlling diaphragm pollution.
The little electrolysis of iron charcoal-Dynamic Membrane advanced treatment of industrial waste water technology that the present invention proposes; Trade effluent is pumped in the little electrolysis pretreatment of the iron charcoal pond; Regulate in the little electrolysis pretreatment of the iron charcoal pond pH value and carry out aeration; Recalcitrant substance in the waste water is degraded to biodegradable material, improves contaminant removal efficiency in the follow-up microbiological treatment process; Afterwards, waste water gets in hydrolysis acidification pool and the aerobic Dynamic Membrane reaction tank, further removes pollutent in the waste water in conjunction with microbiological deterioration processes such as anaerobic hydrolysis-acidification, aerobic oxidations, and the Dynamic Membrane reaction tank need stir, and in Aerobic Pond, carries out aeration; Utilize mixed solution to carry out solid-liquid separation in the Dynamic Membrane that the macropore supporting body surface forms, Dynamic Membrane adopts the mode of permanent flux, change swabbing pressure to move.Concrete steps are following:
(1) the little electrolysis pretreatment of waste water iron charcoal: trade effluent gets in the equalizing tank through fine fack; The pH value that adds waste water in the sour regulating and controlling pond is 4-6; Gained waste water gets in the little electrolysis pretreatment of the iron charcoal pond; The little electrolysis pretreatment of iron charcoal is carried out aeration in the pond, and controlling its dissolved oxygen is 2-3mg/L, and the waste water hydraulic detention time is 0.5-2h; Wherein: the little electrolysis pretreatment of iron charcoal is provided with iron charcoal micro-electrolysis stuffing in the pond; Said iron charcoal micro-electrolysis stuffing is made up of iron filings, Powdered Activated Carbon and rare earth metal powder; The weight ratio of iron filings and Powdered Activated Carbon is 5.6:1-5.7:1, and the add-on of rare earth metal powder is the 0.05-0.09% of iron filings and Powdered Activated Carbon gross weight;
(2) the pH value that adds alkali regulating step (1) water outlet is 7-8, and the water outlet after alkali is regulated is introduced into the coagulation basin coagulation, and the back gets into settling tank and precipitates, hydraulic detention time 8-12min in the dosing coagulant in the coagulation basin, coagulation basin; Adopt swash plate or tube settler to precipitate hydraulic detention time 25-35min in the settling tank;
(3) step (2) gained water outlet gets into hydrolysis acidification pool and aerobic Dynamic Membrane reaction tank, hydrolysis acidification pool hydraulic detention time 3-12h; Aerobic Dynamic Membrane reaction tank dissolved oxygen concentration 2-3mg/L, hydraulic detention time 3-10h; Dynamic film component adopts submerged to be installed in Aerobic Pond, and active sludge intermixture forms Dynamic Membrane through the precoating mode on the dynamic film component surface, and the precoating time is 10-15 minute; Active sludge intermixture filters water outlet through dynamic film component, and control dynamic film component filtration flux is 50-200L/m 2.h, when the dynamic film component transmembrane pressure rose to 30-40kPa, the operation phase finished, and got into the air blast on-line cleaning stage; Adopt 9.8-49 kPa pressure air blast on-line cleaning, gas blower through the outlet conduit air feed from the dynamic film component inner counter to cleaning 2-5min.
Among the present invention; Be enhancement microbiological concentration; Improve pollutent microbiological deterioration efficient and improve Dynamic Membrane composition structure; In active sludge intermixture, add zeyssatite (or zeolite etc.) powder granule thing, form biological reinforced zeyssatite mixed solution (or biological reinforced zeolite mixed solution etc.) and carry out the biological degradation of pollutent in the waste water.
Among the present invention, adding the biological reinforced zeyssatite mixed solution that zeyssatite (or zeolite etc.) forms (or biological reinforced zeolite mixed solution etc.) SS concentration in the said active sludge intermixture of step (3) is 8000-12000mg/L.
Among the present invention, acid is sulfuric acid or hydrochloric acid described in the step (1).
Among the present invention, alkali is lime or sodium hydroxide described in the step (2).
Among the present invention, iron charcoal micro-electrolysis stuffing dosage is put by 10-15/lifting.
Among the present invention, dynamic film component adopts stainless (steel) wire, nylon wire or non-woven fabrics as the dynamic support base net, and the supporter assembly is plate or tubular type, and the aperture of stainless (steel) wire or nylon wire is the 60-80 micron.
Among the present invention, the quantity of said dynamic film component is determined on a case-by-case basis.The dynamic film component sepn process moves continuously; Need each membrane process unit to adopt many cover dynamic film component combined runnings; Wherein always have a cover dynamic film component to be in the on-line cleaning state, a few in addition cover Dynamic Membrane are in running status, guarantee that the total system aquifer yield is stable.
Compare the outstanding feature of present method with traditional technology:
(1) the little electrolysis of iron charcoal-Dynamic Membrane advanced treatment of industrial waste water technology, total system is made up of the little electrolysis pretreatment of iron charcoal, biochemical treatment and Dynamic Membrane stripping technique, and wastewater treatment process is simple, compact, efficient.
(2) the iron charcoal micro-electrolysis stuffing that adds the specific components ratio carries out pre-treatment to trade effluent, can greatly improve the biodegradability of waste water, improves the biodegradable removal efficient of follow-up pollutent.
(3) add the biological reinforced zeyssatite mixed solution that zeyssatite (or zeolite etc.) forms (or biological reinforced zeolite mixed solution etc.) in the mikrobe pond, can greatly improve microbial biomass and microorganism active, and then improve removal effect organic pollutant.
(4) adopt Dynamic Membrane to carry out the mixed solution solid-liquid separation, make the dynamic film component filtration flux can reach 50-200L/m 2.h, and the cycle of operation is long, only needs the air back flushing just can to pollute by controlling diaphragm, need not carry out any matting.
(5) effluent quality after the whole art breading is good, can reach quality of reused water.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Embodiment
Combine accompanying drawing to further specify the present invention through embodiment below.
Embodiment 1
Treatment of dyeing wastewater
Carry out in certain printing and dyeing mill in the implementation process, experiment water-in and water-out water quality is seen shown in the table 1.
 
Table 1 technology water-in and water-out water quality
Project COD(mg/L) pH Colourity (doubly) Ammonia nitrogen (mg/L) Total phosphorus (mg/L)
The former water of equalizing tank 426-580 7.5-8.0 800-1000 30-40 4-7
Little electrolysis pretreatment water outlet 158-207 7.3-8 20 12-14 0.3-0.8
Aerobic Dynamic Membrane water outlet <50 8.02-8.09 <15 1.8-3.6 0.2-0.45
(1) the little electrolysis pretreatment of waste water iron charcoal
Use sulfur waste acid to regulate raw wastewater pH value and be 5-6, get into the reaction tank of filling iron-carbon filling material and carry out aeration, dissolved oxygen is at 2-3mg/L, and the residence time is at 1.5h.After pre-treatment, regulating water outlet pH value is 8-9, behind coagulation basin, settling tank, gets into follow-up microbiological treatment process afterwards.
In the present embodiment, in the iron charcoal micro-electrolysis stuffing of employing, the weight ratio of iron filings and Powdered Activated Carbon is about 5.66:1, and adds and to account for gross weight and be no more than 0.1% rare earth metal powder.
In the present embodiment, iron charcoal micro-electrolysis stuffing dosage is put by 10/lifting.
In the present embodiment, need in the coagulation basin to stir hydraulic detention time 10min; Lime dosage 4kg/ ton waste water; PAM dosage 1g/ ton waste water; Adopt inclined-plate clarifying basin, hydraulic detention time 30min.
(2) Dynamic Membrane reaction tank pollutent biological degradation
In the present embodiment, the SS concentration of in active sludge, adding the biological reinforced zeyssatite mixed solution of zeyssatite formation is about 10000mg/L.
In the present embodiment, hydrolysis acidification pool hydraulic detention time 10h.
In the present embodiment, Aerobic Pond dissolved oxygen 2-3mg/L, time 10h.
In the present embodiment, discharge a certain amount of mixed solution every day from reaction tank, sludge retention time is maintained about 20d, and the diatomaceous weight additional according to material balance calculating needs.
(3) mixed solution solid-liquid separation
Dynamic film component adopts submerged to be installed in the Aerobic Pond.The biological diatomite mixed solution forms Dynamic Membrane through the precoating process on the dynamic film component surface, and the precoating time is 10-15 minute, and water outlet this moment suspended solids can not detect or turbidity≤1 NTU; Afterwards, dynamic film component filters water outlet, and control dynamic film component filtration flux is 80L/m 2.h.When the dynamic film component transmembrane pressure rose to 40kPa, the operation phase finished, and got into the air blast on-line cleaning stage.Adopt 49 kPa pressure air blast on-line cleaning, carry out gas blower through the outlet conduit air feed from the dynamic film component inner counter to cleaning 4min.
In the present embodiment, dynamic film component supporting network employing equivalent aperture is 75 microns a stainless (steel) wire, and the supporter assembly is plate.
In the present embodiment, the dynamic film component sepn process moves continuously, adopts 5 cover dynamic film component combined runnings, wherein always has a cover dynamic film component to be in the on-line cleaning state, and other 4 cover dynamic film components are in running status, guarantee that the total system aquifer yield is stable.
Embodiment 2:
Treatment of Coking Effluent
Test the water outlet after used coking chemical waste water is taken from certain Coking Plant Wastewater secondary biochemical treatment, carry out advanced treatment as the water inlet of this technology.The experiment water-in and water-out water quality of this technology is seen shown in the table 2 in the implementation process.
 
Table 1 technology water-in and water-out water quality
Project pH COD(mg/L) Ammonia nitrogen (mg/L) TN (mg/L) TP (mg/L) Colourity/doubly
Test former water 6.8-8.5 330-450 10.4-25.4 43.2-81.3 0.8-1.9 200-300
Little electrolysis pretreatment water outlet 5.1-5.5 198-260 8.9-22.1 36.2-68.1 0.35-0.6 14-18
Aerobic Dynamic Membrane water outlet 8.1-8.5 <50 <2.3 <15 <0.1-0.2 13-18
(1) the little electrolysis pretreatment of waste water iron charcoal
Regulate former water pH value with sulfur waste acid and be about 4, get into the reaction tank of filling iron-carbon filling material and carry out aeration, dissolved oxygen is at 2-3mg/L, and the residence time is at 1.5h.After pre-treatment, regulating water outlet pH value is 8-9, behind coagulation basin, settling tank, gets into follow-up microbiological treatment process afterwards.
In the present embodiment, in the iron charcoal micro-electrolysis stuffing of employing, the weight ratio of iron filings and Powdered Activated Carbon is about 5.66:1, and adds and to account for gross weight and be no more than 0.1% rare earth metal powder.
In the present embodiment, iron charcoal micro-electrolysis stuffing dosage is put by 10/lifting.
In the present embodiment, need in the coagulation basin to stir hydraulic detention time 10min; Lime dosage 3kg/ ton waste water; PAM dosage 1g/ ton waste water; Adopt inclined-plate clarifying basin, hydraulic detention time 30min.
(2) Dynamic Membrane reaction tank pollutent biological degradation
In the present embodiment, the SS concentration of in active sludge, adding the biological reinforced zeyssatite mixed solution of zeyssatite formation is about 8000mg/L.
In the present embodiment, hydrolysis acidification pool hydraulic detention time 3h.
In the present embodiment, Aerobic Pond dissolved oxygen 2-3mg/L, time 3h.
In the present embodiment, discharge a certain amount of mixed solution every day from reaction tank, sludge retention time is maintained about 20d, and the diatomaceous weight additional according to material balance calculating needs.
(3) mixed solution solid-liquid separation
Dynamic film component adopts submerged to be installed in the Aerobic Pond.The biological diatomite mixed solution forms Dynamic Membrane through the precoating process on the dynamic film component surface, and the precoating time is 10-15 minute, and water outlet this moment suspended solids can not detect or turbidity≤1 NTU; Afterwards, dynamic film component filters water outlet, and control dynamic film component filtration flux is 80L/m 2.h.When the dynamic film component transmembrane pressure rose to 40kPa, the operation phase finished, and got into the air blast on-line cleaning stage.Adopt 49 kPa pressure air blast on-line cleaning, carry out gas blower through the outlet conduit air feed from the dynamic film component inner counter to cleaning 4min.
In the present embodiment, dynamic film component supporting network employing equivalent aperture is 75 microns a stainless (steel) wire, and the supporter assembly is plate.
In the present embodiment, the dynamic film component sepn process moves continuously, adopts 3 cover dynamic film component combined runnings, wherein always has a cover dynamic film component to be in the on-line cleaning state, and other 4 cover dynamic film components are in running status, guarantee that the total system aquifer yield is stable.

Claims (6)

1. the little electrolysis of iron charcoal-Dynamic Membrane advanced treatment of industrial waste water technology is characterized in that concrete steps are following:
(1) the little electrolysis pretreatment of waste water iron charcoal: trade effluent gets in the equalizing tank through fine fack; The pH value that adds waste water in the sour regulating and controlling pond is 4-6; Gained waste water gets in the little electrolysis pretreatment of the iron charcoal pond; The little electrolysis pretreatment of iron charcoal is carried out aeration in the pond, and controlling its dissolved oxygen is 2-3mg/L, and the waste water hydraulic detention time is 0.5-2h; Wherein: the little electrolysis pretreatment of iron charcoal is provided with iron charcoal micro-electrolysis stuffing in the pond; Said iron charcoal micro-electrolysis stuffing is made up of iron filings, Powdered Activated Carbon and rare earth metal powder; The weight ratio of iron filings and Powdered Activated Carbon is 5.6:1-5.7:1, and the add-on of rare earth metal powder is the 0.05-0.09% of iron filings and Powdered Activated Carbon gross weight;
(2) the pH value that adds alkali regulating step (1) water outlet is 7-8, and the water outlet after alkali is regulated is introduced into the coagulation basin coagulation, and the back gets into settling tank and precipitates, hydraulic detention time 8-12min in the dosing coagulant in the coagulation basin, coagulation basin; Adopt swash plate or tube settler to precipitate hydraulic detention time 25-35min in the settling tank;
(3) step (2) gained water outlet gets into hydrolysis acidification pool and aerobic Dynamic Membrane reaction tank, hydrolysis acidification pool hydraulic detention time 3-12h; Aerobic Dynamic Membrane reaction tank dissolved oxygen concentration 2-3mg/L, hydraulic detention time 3-10h; Dynamic film component adopts submerged to be installed in Aerobic Pond, and active sludge intermixture forms Dynamic Membrane through the precoating mode on the dynamic film component surface, and the precoating time is 10-15 minute; Active sludge intermixture filters water outlet through dynamic film component, and control dynamic film component filtration flux is 50-200L/m 2.h, when the dynamic film component transmembrane pressure rose to 30-40kPa, the operation phase finished, and got into the air blast on-line cleaning stage; Adopt 9.8-49 kPa pressure air blast on-line cleaning, gas blower through the outlet conduit air feed from the dynamic film component inner counter to cleaning 2-5min.
2. treatment process according to claim 1; It is characterized in that adding in the said active sludge intermixture of step (3) the biological reinforced zeyssatite mixed solution or the biological reinforced zeolite mixed solution of zeyssatite or zeolite formation, the biological reinforced zeyssatite mixed solution or the biological reinforced zeolite mixed solution SS concentration of adding the formation of zeyssatite or zeolite are 8000-12000mg/L.
3. treatment process according to claim 1 is characterized in that acid described in the step (1) is sulfuric acid or hydrochloric acid.
4. treatment process according to claim 1 is characterized in that alkali is lime or sodium hydroxide described in the step (2).
5. treatment process according to claim 1 is characterized in that iron charcoal micro-electrolysis stuffing dosage puts by 10-15/lifting.
6. treatment process according to claim 1 is characterized in that dynamic film component adopts stainless (steel) wire, nylon wire or non-woven fabrics as the dynamic support base net, and the supporter assembly is plate or tubular type, and the aperture of stainless (steel) wire or nylon wire is the 60-80 micron.
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