CN101654314A - Dye waste water treatment method - Google Patents
Dye waste water treatment method Download PDFInfo
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- CN101654314A CN101654314A CN200910092258A CN200910092258A CN101654314A CN 101654314 A CN101654314 A CN 101654314A CN 200910092258 A CN200910092258 A CN 200910092258A CN 200910092258 A CN200910092258 A CN 200910092258A CN 101654314 A CN101654314 A CN 101654314A
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Abstract
The invention provides a dye waste water treatment method, comprising a materializing pre-treatment, an anaerobic treatment, an aerobic treatment, and an advanced oxidation treatment carried out in sequence, wherein the method comprises the steps of conducting a materializing pre-treatment to the object dye waste water to get rid of a part of chromaticity and COD for the anaerobic treatment and aerobic treatment, and then conducting an advanced oxidation treatment to the water discharged from the aerobic treatment to finally remove the degradation-refractory pollutant at the end of the waste water treatment and the intermediate metabolized substances produced in the process of biological treatment. Through the combined process of materializing pre-treatment, anaerobic treatment, aerobic treatment and advanced oxidation treatment, the invention can effectively treat difficultly degraded dye waste water and reduce the operation cost, thereby being capable of standardizing the indexes such as COD and chromaticity of the discharged water to the national norm simultaneously, solving the domestic current situation of difficulties in treating dye waste water, and being capable of meetingthe requirements of upgrading and restructuring the sewage treatment plant according to the increased standard of environment protection in the future.
Description
Technical field
The present invention relates to technical field of waste water processing, particularly relate to a kind of waste water from dyestuff and other high salinity, high-sulfate, high chroma, high COD and contain the method for wastewater treatment of higher concentration hardly degraded organic substance.
Background technology
Since British W.H.Perking in 1857 made first synthetic dyestuff mauvein (e), dyestuffs industries had become one of important industry of fine chemistry industry industry, was bringing into play important effect in the national economy life.Along with the development of dyestuffs industries, waste water from dyestuff has been acknowledged as one of current main pollution source of water body, environmental issue thereby also become the important factor of restriction dyestuff industry development.Waste water from dyestuff not only has specific color, and complex structure, is difficult to break, and biological degradability is low, mostly has genotoxic potential, and returning in environment becomes to depending on a lot of X factors.The kind of dyestuff is various day by day in addition, and the requirement that adapts to market develops towards directions such as anti-photodissociation, anti-oxidant, antibiont degradeds, causes the intractability of waste water from dyestuff also to increase the weight of gradually.
In general, waste water from dyestuff has high chroma, high COD, supersalinity, low BOD
5" three high one is low " characteristics of/COD, and water quality and quantity changes greatlyyer in time, belongs to more unmanageable organic industrial sewage.According to estimates, nearly 90% inorganic raw material and 10～30% organic raw material are transferred to aqueous phase in the DYE PRODUCTION process, so the waste water from dyestuff complicated component, and the pollution concentration height generally has following characteristics:
(1) the organism overwhelming majority in the waste water be with aromatophores such as benzene, naphthalene, anthracene, quinones as parent, and have the colour developing group, color is darker, colourity can reach 500～500000 times.
(2) basic raw material of DYE PRODUCTION is organism such as benzene series, naphthalene system, anthraquinone system, and product yield is low, and the dyestuff rate of loss is about 2% in the production process, causes in the waste water COD concentration higher, generally can reach 1000～73000mg/L.And the most key be, though partial organic substances can be biochemical in the waste water from dyestuff, BOD
5/ COD ratio is totally lower, and biodegradability is relatively poor, and the some of them material is to microorganism even also have a toxic action.
(3) waste water is acid more, also has to be alkalescence.Owing to adopt the way of saltouing that dye preparations is purified in the DYE PRODUCTION process usually, so generally all contain NaCl, Na in the waste water from dyestuff
2SO
4, Na
2Inorganic salts such as S, and saltiness is bigger.
(4) also contain a considerable amount of suspended particulates, dispersion agent and a small amount of heavy metal ion in the waste water from dyestuff.
(5) because DYE PRODUCTION technology has characteristics such as wide in variety, long flow path, variation are many, the water quality of waste water and water yield fluctuation are all bigger.
The treatment process of waste water from dyestuff mainly contains: biological treatment, chemical oxidation, photochemical catalysis, membrane sepn, electrochemistry, chemical flocculation, adsorption decoloring method etc.But because the dyestuffs industries factory effluent has the characteristics of " three high is low ", of a great variety, the water quality and quantity of adding dyestuff change greatly in time, thereby single a kind of technology is difficult to obtain satisfied effect.Handle waste water containing dye at present, it is the associating multilevel processing technology axle center, that combine with physical chemistry or chemical process that treatment process is progressively turning to the anaerobic-aerobic combination treatment, make every effort to replenish, to remedy physical chemistry method and biological method defective separately by the mutual coordination between materialization and the biological method.And the associating multilevel processing technology that present employed physical chemistry or chemical process combine adopts the method for physico-chemical pretreatment and anaerobic-aerobic combined treatment more, the general coagulant sedimentations that adopt of physico-chemical pretreatment more, and the single employing of pre-treatment coagulating sedimentation single method dosage is big, cost is high, does not reach the required pH of follow-up anaerobic treatment, basicity and suitable sulfate concentration.The associating multilevel processing technology that has also has after aerobic treatment and carries out aftertreatment with coagulant sedimentation, and the single coagulating sedimentation single method dosage that adopts of aftertreatment is big, the cost height, water outlet after the processing can't reach the primary standard in " GB4287-92 textile dyeing and finishing emission of industrial pollutants standard ", and the aforesaid combination method is at high salinity, high-sulfate, high chroma, high COD and to contain the treatment effect of waste water from dyestuff of higher concentration hardly degraded organic substance not good, some poisonous and harmful in the waste water from dyestuff, the organic compound that chemical property is more stable, utilize biodegradable method often to be difficult to handle, by coagulation technology mainly is by physical means the organic pollutant in the water body to be separated, and does not change the form and the character of pollutent.
Summary of the invention
In order to solve the above-mentioned problems in the prior art, the invention provides a kind of dye waste water treatment method, this method can effectively be handled the difficult degradation waste water from dyestuff, reduce running cost, make indexs such as the COD of water outlet and colourity can reach national specified discharge standard simultaneously, solve the unmanageable at home present situation of waste water from dyestuff, and can satisfy that environmental protection standard in the future improves and the requirement of sewage work's upgrading.
Technical scheme of the present invention is as follows:
A kind of dye waste water treatment method, comprise the physico-chemical pretreatment of carrying out successively, anaerobic treatment, aerobic treatment, pending waste water from dyestuff is carried out earlier carrying out anaerobic treatment and aerobic treatment after physico-chemical pretreatment is removed a part of colourity and COD, water outlet discharging after the processing or reuse after further handling, it is characterized in that: also comprise the advanced oxidation processing, described advanced oxidation treatment step is arranged on after the aerobic treatment step, advanced oxidation is carried out in the water outlet after the aerobic treatment handle so that finally remove the intermediate metabolites that produces in the difficult degradation pollutent of wastewater treatment end and the biological treatment process.
The concrete steps that described advanced oxidation is handled are as follows:
(1) interior electrolytic reaction: the interior electrolytic reaction of interior electrolyzer generation of loading iron plane flower and gac is according to a certain percentage introduced in the water outlet after the aerobic treatment further removed colourity and COD, described waste and old iron plane flower is to constitute macroscopical electrode with described gac by the body material of interior electrolytic reaction;
(2) oxidizing reaction: replenish proper amount of oxidant in the water outlet after interior electrolytic reaction, remove colourity and COD by oxidation, precipitating action;
(3) coagulating sedimentation: add saturated limewater and regulate pH value water outlet qualified discharge to neutrality, the coagulating sedimentation.
The described physico-chemical pretreatment stage comprises the steps:
(1) interior electrolytic reaction: pending waste water from dyestuff is introduced the interior electrolytic reaction of interior electrolyzer generation of loading iron plane flower and coke according to a certain percentage remove a part of colourity and COD, described waste and old iron plane flower is to constitute macroscopical electrode with described coke by the body material of interior electrolytic reaction;
(2) coagulating sedimentation: the adding saturated limewater is regulated the pH value, coagulating sedimentation is removed most vitriol, colourity and COD.
Described iron plane flower and the filling of gac volume are than being 2: 1, and described iron plane flower and the filling of coke volume are than being 2: 1, and ventilation recoil automatically in the electrolytic reaction step makes gas-water ratio remain on 10: 1-20: 1 in described; Also add polymerize aluminum chloride and polyacrylamide in the coagulating sedimentation step in described physico-chemical pretreatment stage, the enhanced coagulation precipitation is removed most of colourity and COD in the waste water.
Add before the interior electrolytic reaction treatment stage of described advanced oxidation useless acid for adjusting pH value to 3-4 in case reach carry out in the optimal ph of electrolytic reaction, carry out described in electrolytic reaction 1-2 hour.
Described oxygenant is 30% hydrogen peroxide, and the hydrogen peroxide dosage is 1-2ml/L, reacts 2-3 hour, adds saturated limewater adjusting pH value and added the polyacrylamide precipitation again 1-2 hour to neutrality.
Adopt upflow anaerobic sludge blanket process in described anaerobic treatment stage, and inoculation anaerobic grain sludge, carry out 4-6 month anaerobion domestication, and add engineering bacteria and eliminate in the waste water ammonia nitrogen and sulfide the influence of methanogen, chemistry, the biological respinse of a series of complexity takes place in the process anaerobion, removes colourity and also makes the anaerobism effluent quality help the degraded of aerobic microbiological more.
In described aerobic treatment used carrier be can fixation of microbe the urethane carrier, microbe inoculation is the similar waste water active sludge of pending waste water from dyestuff, and add engineering bacteria and carry out biochemical intensive treatment, the required dissolved oxygen of aerobic reaction is 3-5mg/L.
Carry out after the described physico-chemical pretreatment heating as required before the anaerobic treatment and regulating the pH value to follow-up anaerobic treatment stage required temperature and pH value, adjusting the pH value is that 6.5-7.0, temperature are 25 ℃-40 ℃, and according to carrying out anaerobic reaction behind the additional an amount of trace element of water quality situation.
Electrolytic reaction step and aerobic treatment stage are by the gas blower oxygen supply in described; The precipitating sludge that described coagulating sedimentation step, anaerobic treatment step produce is pressed into the mud cake outward transport.
Technique effect of the present invention is:
The present invention will carry out successively water outlet after physico-chemical pretreatment, anaerobism, the aerobic treatment carry out advanced treatment by advanced oxidation processes in case finally remove the difficult degradation pollutent of wastewater treatment end and biological treatment process in the intermediate metabolites that produces.Advanced oxidation processes produces hydroxyl radical free radical (OH) by reaction, and utilizing the strong oxidized form of OH can be nontoxic material with oxidation operation, even directly with inorganicization of organism, is oxidized to CO2 and H2O, reaches the purpose that alleviates or eliminate water pollution.The present invention adopts the combination process of " physico-chemical pretreatment+anaerobism+aerobic+advanced oxidation " to come dye wastewater treatment using, remove most colourity, vitriol and COD by strengthening pre-treatment, guarantee required pH, basicity and the suitable sulfate concentration of back segment anaerobic technique efficient stable operation, reduce operating cost for back end processing; Make indexs such as the COD of water outlet and colourity can reach national specified discharge standard or reuse after further processing simultaneously by strengthening aftertreatment, solve the unmanageable at home present situation of waste water from dyestuff, and can satisfy the requirement of environmental protection standard raising in the future sewage work's upgrading.This combination process is for waste water from dyestuff, especially high salinity, high-sulfate, high chroma, high COD and contain the waste water of higher concentration hardly degraded organic substance, has good treatment effect, final outflow water can reach the primary standard in " GB4287-92 textile dyeing and finishing emission of industrial pollutants standard ", and because COD, colourity concentration in the technology water outlet are very low, make up the proper depth treatment process on this basis, water outlet can be satisfied the water quality requirement of associated cyclic water coolant or other reuse water, realize waste water reclaiming, reach the purpose that industry energy conservation reduces discharging.
Advanced oxidation processes of the present invention adopts the multiple-stage treatment mode, promptly interior electrolysis, oxidizing reaction and coagulating sedimentation.On the basis of coagulating sedimentation step by set up improve in electrolysis process, electrolysis process can produce the Fe2+ of capacity in the aeration under acidic conditions, can save adding of FeSO4 in the Fenton reagent, greatly reduces running cost.Interior electrolytic reaction produces a certain amount of Fe2+ ion, form strong oxidation system--Fenton reagent with the oxygenant of follow-up interpolation, raising is guaranteed discharged wastewater met the national standard to the removal effect of hardly degraded organic substance and colourity, and can satisfy the requirement of environmental protection standard raising in the future to sewage work's upgrading.The oxygenant that adopts among the present invention is 30% hydrogen peroxide, hydrogen peroxide (H2O2) produces a large amount of hydroxyl radical free radicals (OH) under the katalysis of Fe2+, OH is as a kind of strong oxidizer, organism that can the multiple difficult degradation of oxidation, be converted into CO2 and H2O, can not produce secondary pollution (handle waste water as Cl2 and easily produce haloform class by product (THMs), cause secondary pollution).
Physico-chemical pretreatment adopts the multistage pretreatment mode to waste water, electrolysis and coagulating sedimentation promptly, interior electrolysis process can be good at reducing the colourity and the COD of dye wastewater with high concentration, improves the biodegradability of waste water simultaneously, for better condition is created in follow-up biological treatment.Add saturated limewater, the Fe that electrolysis produces in making on the one hand
2+And Fe
3+Under alkaline condition, form efficient flocculant, the colourity and the COD of waste water removed, on the other hand the Ca in the liming
2+With the SO in the waste water
4 2-Form calcium sulfate precipitation, greatly reduce sulfate concentration in the former water, help the raising of anaerobic treatment effect and treatment capacity; In addition, calcium hydroxide itself also is a kind of inorganic flocculating agent, can remove the colourity and the COD of waste water effectively.According to the waste water quality situation, optionally add polymerize aluminum chloride and polyacrylamide, waste water is carried out the enhanced coagulation precipitation, reduce the load of follow-up biochemical processing unit, reduce the running cost of biochemical treatment.
Adopt ventilation recoil automatically in the interior electrolysis treatment process during physico-chemical pretreatment and advanced oxidation are handled, promptly adopt pneumatic blending, wherein gas-water ratio is 10: 1-20: 1, the settling that reaction generates in the electrolyzer in can making like this can be flushed away timely and effectively, eliminate the factor and the hidden danger that produce the iron filings caking, moreover, because the iron filings surface deposits is flushed away at any time, thereby make its surface and waste water keep excellent contact, can greatly improve electrode reaction.
Anaerobic treatment stage adopts upflow anaerobic sludge blanket process, inner inoculation anaerobic grain sludge, and add engineering bacteria and eliminate in the waste water ammonia nitrogen and sulfide the influence of methanogen, chemistry, the biological respinse of a series of complexity takes place in the process anaerobion, removes colourity and also makes the anaerobism effluent quality help the degraded of aerobic microbiological more.Biogas and mud that anaerobism produces separate through triphase separator.Waste water from dyestuff under anaerobic opens the two keys of azo by the effect of azo reductase, can finish most decolorization and partial C OD degradation process.
In the aerobic treatment used carrier be can fixation of microbe the urethane carrier, immobilized microorganism technique is with chemistry or physical means the free microorganism activity to be defined in certain area of space, and make it keep method active, that recycle, compare with free microorganism, immobilized microorganism demonstrates advantages such as microbe density height, speed of response are fast, microorganism is run off less, product separates easily, reaction process control is easier to significantly.The carrier of fixation of microbe has characteristics such as reactivity, wetting ability, permeability, high-specific surface area, and has space cantilever and network cross-linked structure, can form valence link and combine with microorganism, enzyme, and carrier and microorganism are combined closely and can reduce the microorganism number of dropouts.Solid support material has amino, carboxyl, epoxy group(ing) isoreactivity group, has satisfactory stability and physical and chemical performance in sewage, and its voidage is more than 96%, and the density behind the immobilized microorganism approaches the density of water, so be suspension in water.Therefore contaminant degradation speed is fast, strong shock resistance, processing efficiency height, system stability and good denitrogenation and dephosphorization effect.Microbe inoculation is the similar waste water active sludge of pending waste water from dyestuff, adopts this efficient special microorganism, and is fast to organic matter degradation speed, ammonia nitrogen removal effect uniqueness.Add engineering bacteria and carry out biochemical intensive treatment.
Description of drawings
Fig. 1 is a process flow sheet of the present invention;
Fig. 2 is dye waste water treatment system figure of the present invention.
Embodiment
The present invention will be further described below in conjunction with accompanying drawing.Fig. 1 is a process flow sheet of the present invention, and Fig. 2 is dye waste water treatment system figure of the present invention.
The invention provides a kind of dye waste water treatment method, as shown in Figure 1, adopt the combination process (hereinafter to be referred as the PUBA combination process) of " physico-chemical pretreatment+anaerobism+aerobic+advanced oxidation " to come dye wastewater treatment using.Can in the physico-chemical pretreatment system+anaerobic pond that sets gradually+Aerobic Pond+advanced oxidation treatment system, handle pending waste water from dyestuff.As shown in Figure 2, the physico-chemical pretreatment system comprises the interior electrolyzer that sets gradually, preceding coagulative precipitation tank, and the advanced oxidation treatment system comprises interior electrolyzer, oxidation pond, the back coagulative precipitation tank that sets gradually.A part of colourity and COD are removed in electrolytic reaction in carrying out behind the electrolytic reaction pond in the pending waste water from dyestuff introducing, preceding coagulative precipitation tank is introduced in the water outlet of interior electrolytic reaction pond regulated the pH value, coagulating sedimentation is removed most vitriol, colourity and COD, after enter anaerobic pond generation anaerobic reaction and remove colourity and make the anaerobism effluent quality help the degraded of aerobic microbiological more, waste water is carried out a biological disposal upon through the Aerobic Pond that enters the rear end after the anaerobic treatment, outputted aerobic water is carried out advanced treatment by improved advanced oxidation processes, and water outlet can qualified discharge or reuse after further handling.
Between preceding coagulative precipitation tank and anaerobic pond, dosing chamber can be set preferably, in dosing chamber heating and regulate the pH value to follow-up anaerobic treatment stage required temperature and pH value, adjusting the pH value is that 6.5-7.0, temperature are 25 ℃-40 ℃, and according to carrying out anaerobic reaction behind the additional an amount of trace element of water quality situation.
The concrete steps of dye waste water treatment method of the present invention are as follows:
In the P section physico-chemical pretreatment stage, electrolysis in adopting, adjusting pH and coagulation-settlement process, make in the waste water most colourity, vitriol and COD obtain removing, guaranteed required pH, basicity and the suitable sulfate concentration of back segment anaerobic technique efficient stable operation.In interior electrolytic reaction pond, adopt the body material of waste and old iron plane flower as reaction, add a small amount of coke and constitute macroscopical electrode, iron plane flower and coke volume load than being 2: 1.The settling that generates for reaction in the electrolyzer in making can be flushed away timely and effectively, eliminates the factor and the hidden danger that produce the iron filings caking, adopts ventilation recoil automatically in treating processes, promptly adopts pneumatic blending, and wherein gas-water ratio is 10: 1-20: 1.Because the iron filings surface deposits is flushed away at any time, thereby make its surface and waste water keep excellent contact, can greatly improve electrode reaction.In interior electrolytic reaction pond, can reach 25-30%, color removal 40-50% to the removal efficient of COD.Waste water adds saturated limewater and regulates pH through after the interior electrolytic reaction, removes most vitriol in the waste water, adds polymerize aluminum chloride and polyacrylamide simultaneously, and the enhanced coagulation precipitation is removed most of colourity and COD in the waste water.In the coagulating sedimentation step, COD is removed efficient and can reach 50-60%, color removal 60-65%, vitriol is removed 50-55%.
In U section anaerobic treatment stage, the anaerobic reactor in anaerobic pond adopts the technology of upflow anaerobic sludge blanket process UASB structure to carry out anaerobic treatment, and mainly colourity and the COD to waste water handles.Water inlet pH is controlled at 6.5-7.0, temperature about 30 ℃, according to the water quality situation, enters anaerobic pond behind the additional an amount of trace element and carries out anaerobic reaction.Through the anaerobion domestication of some months, finally the clearance to colourity can reach more than 80%, also makes the anaerobism effluent quality help the degraded of aerobic microbiological more simultaneously.Inoculation anaerobic grain sludge in the UASB reactor, and add engineering bacteria B120, ammonia nitrogen and sulfide are to the influence of methanogen in the elimination waste water, and the original strain of engineering bacteria is provided by the BIO-SYSTEMS company of the U.S..
In the B section aerobic treatment stage, adopt immobilized microorganism-BAF G-BAF aerobic treatment unit, remove most ammonia nitrogen and COD in the waste water, dissolved oxygen is 3-5mg/L, the COD clearance is 45-50%.G-BAF adopts immobilized microorganism technique, used efficient suspension macropore carrier (CN2004100625771), wherein institute's microbe inoculation is similar waste water active sludge, and adds engineering bacteria and carry out biochemical intensive treatment, and the original strain of engineering bacteria is provided by the BIO-SYSTEMS company of the U.S..Add the high-effective microorganism carrier of the 30-60% that accounts for the aeration tank useful volume in the G-BAF reactor, the special efficacy microorganism adheres in large quantities and fixes on it, and the G-BAF reactor is actually the twin thing reactor of comprehensive traditional activated sludge process and biomembrance process advantage.In the G-BAF reactors at different levels,, improve the degradation effect of target contaminant by cultivating different special efficacy bacterial classifications; The biomass that surfaces of carrier materials is grown is generally 18-25g/L, be common biomembrance process 1.5-2.0 doubly, be traditional activated sludge process 10-20 doubly, and microorganism combines with carrier firmly, difficult drop-off, be difficult for running off, the biomass of high capacity has guaranteed the efficient and stable of G-BAF reactor removal pollutent; Carrier inside exists good anaerobic zone microenvironment in the operational process, make the numerous miniature denitrification reactor of its inner formation, ammonia oxidation, nitrification and denitrification combined action take place in the middle of same reactor simultaneously so cause, strong assurance the efficient removal of ammonia nitrogen; By controlling the operating parameter of G-BAF reactors at different levels, cause the existence of the aerobic and anaerobic environment of macroscopic view, help releasing phosphorus and excessively taking the photograph phosphorus of polyP bacteria, guaranteed the removal of phosphorus.G-BAF technology core processing structures are BAF, and the pond body is the sheet water flow mode of pressure reduction turnover plate type in form, can be designed to circle or rectangle according to practical situation, and aeration mode is an aeration at the bottom of the air blast pond.The G-BAF pond partly is made up of pond body, high-effective microorganism carrier, interception net and aeration tube etc.The microbial fixed carrier that immobilized microorganism-BAF (G-BAF) high-efficiency sewage treatment process is adopted is a kind of high molecular synthetic material with netted macroporous structure, have characteristics such as reactivity, wetting ability, permeability, high-specific surface area, and have space cantilever and network cross-linked structure, can form valence link and combine with microorganism, enzyme.G-BAF technology also has the advantage of stable effluent quality under the high loading water inlet, and pollutant removal amount and clearance all increase with the raising of influent concentration, shows G-BAF and adapts to the ability of handling high-concentration waste water, and its special advantages is especially arranged aspect denitrogenation.Therefore, adopt G-BAF technology that the device volume is significantly reduced, thereby reduce the soil occupied area, reduce construction costs.
The treatment stage of A section advanced oxidation, effectively remove colourity and hardly degraded organic substance in the waste water, by regulating wastewater pH, after electrolyzer carries out interior electrolytic reaction in the process aeration, replenish proper amount of oxidant, by oxidation, precipitating action, effectively remove colourity and hardly degraded organic substance (comprising the intermediate metabolites that produces in the biological treatment process) in the waste water.Concrete steps are: outputted aerobic water adds spent acid and regulates pH to 3-4, enters the interior electrolyzer at rear portion, stops 1-2 hour.By interior electrolytic reaction, further remove the COD and the colourity of waste water, simultaneously interior electrolytic reaction can also produce a certain amount of Fe
2+Ion is formed strong oxidation system--Fenton reagent with the hydrogen peroxide of follow-up interpolation.Interior electrolysis water outlet adds 30% hydrogen peroxide 1-2ml/L, at the reaction tank internal reaction after 2-3 hour, adds saturated limewater and regulates pH to neutral, adds behind the coagulant aids in precipitation in the settling tank after 1-2 hour the water outlet qualified discharge.When BAF water outlet COD is 500mg/L, pH is 7.5, when colourity is 600 times, by adding the sulfur waste acid for adjusting pH to 3-4, stopped 2 hours by interior electrolytic reaction, 30% hydrogen peroxide dosage is 2ml/L afterwards, reacts 2 hours, precipitate after 2 hours, water outlet COD is less than 70mg/L, and colourity is less than 20 times.
Purposes of the present invention is not only applicable to the upgrading of dye wastewater treatment and existing sewage treatment project, and is applicable to other high salinity, high-sulfate, high chroma, high COD and contains the wastewater treatment of higher concentration hardly degraded organic substance.
Enumerate two examples below the present invention is further specified, but the present invention is not limited to this two examples.
Adopt the PUBA combination process that certain dye chemical industry factory waste water is carried out lab scale research.The COD of waste water, total salinity, vitriol and colourity are respectively 5000-6000mg/L, 90000-100000mg/L, 10000-12000mg/L and 35000-40000 doubly.Because former salinity water is too high, through after the suitable dilution, enter the pretreatment technology unit after, COD, vitriol and colourity are reduced to 1000-1500mg/L, 800-1000mg/L and 4000-5000 respectively doubly.Through anaerobic treatment, the residence time was made as 20 hours, and water outlet COD and colourity are respectively 600-800mg/L and 400-500 doubly.The anaerobism water outlet enters the BAF reaction column, and the residence time is 8 hours, and water outlet COD and colourity are respectively 300-350mg/L and 200-250 doubly.Outputted aerobic water enters the advanced oxidation processes section, by adding acid for adjusting pH to 3-4, stops 1 hour by interior electrolytic reaction, and 30% hydrogen peroxide dosage is 1ml/L afterwards, reacts 2 hours, and COD is less than 50mg/L in the post precipitation water outlet, and colourity is less than 10 times.Wherein anaerobic reactor is inoculated certain W-Gum factory anaerobic grain sludge, cultivates 2 months to the bacterial classification maturation, and decolorizing efficiency reaches 80%.BAF add engineering bacteria (350M and 110 two kinds) carry out biological reinforced, to improve removal efficient to hardly degraded organic substance.
Certain dye chemical industry factory, main products is dyestuff intermediate DSD acid.Mainly contain band nitro, amino and sulfonic aromatic organic compounds in the waste water, belong to the high concentrated organic wastewater of difficult degradation, concrete water quality analysis is as shown in table 1.
The table 1 influent quality water yield
| Sequence number | Project | Influent quality | Unit |
| ??1 | The water yield | ??500 | ??m 3/d |
| ??2 | ??COD Cr | ??6865.3 | ??mg/L |
| ??3 | Salinity | ??65772.5 | ??mg/L |
| ??4 | ??SO 4 2- | ??26323.5 | ??mg/L |
| ??5 | Colourity | ??50000 | |
| ??6 | ??pH | ??3 |
Adopt the described PUBA combination process of specification sheets, this waste water from dyestuff is handled, day output is 500m
3/ d.Wherein the UASB reactor and the BAF pond residence time were respectively 24 hours and 12 hours, and seed sludge comes from Shandong W-Gum factory anaerobic grain sludge and and dye processing plant, Henan active sludge respectively.Engineering examination up to standard is so far with steady running more than 1 year, and whole combination process has been obtained the stable treated effect, and the treatment effect of each technique unit is as shown in table 2.
Table 2 main technique unit water quality (unit: mg/L, colourity does not have unit)
By above-mentioned example as can be seen, no matter be that lab scale experiment or engineering are used, the present invention is for waste water from dyestuff, especially high salinity, high-sulfate, high chroma, high COD and contain the waste water of higher concentration hardly degraded organic substance, have good treatment effect, final outflow water can reach the primary standard in " GB4287-92 textile dyeing and finishing emission of industrial pollutants standard ".And, because COD, the colourity concentration of the water outlet of PUBA technology are very low, make up proper depth treatment process (as reverse osmosis desalination etc.) on this basis, water outlet can be satisfied the water quality requirement of associated cyclic water coolant or reuse water fully, realize waste water reclaiming, reach the purpose that industry energy conservation reduces discharging.
The above only is a preferred implementation of the present invention, and other modification and the improvement for making according to essence of the present invention all will fall into protection scope of the present invention.
Claims (10)
1. dye waste water treatment method, comprise the physico-chemical pretreatment of carrying out successively, anaerobic treatment, aerobic treatment, pending waste water from dyestuff is carried out earlier carrying out anaerobic treatment and aerobic treatment after physico-chemical pretreatment is removed a part of colourity and COD, water outlet discharging after the processing or reuse after further handling, it is characterized in that: also comprise the advanced oxidation processing, described advanced oxidation treatment step is arranged on after the aerobic treatment step, advanced oxidation is carried out in the water outlet after the aerobic treatment handle so that finally remove the intermediate metabolites that produces in the difficult degradation pollutent of wastewater treatment end and the biological treatment process.
2. dye waste water treatment method according to claim 1 is characterized in that: the concrete steps that described advanced oxidation is handled are as follows:
(1) interior electrolytic reaction: the interior electrolytic reaction of interior electrolyzer generation of loading iron plane flower and gac is according to a certain percentage introduced in the water outlet after the aerobic treatment further removed colourity and COD, described waste and old iron plane flower is to constitute macroscopical electrode with described gac by the body material of interior electrolytic reaction;
(2) oxidizing reaction: replenish proper amount of oxidant in the water outlet after interior electrolytic reaction, remove colourity and COD by oxidation, precipitating action;
(3) coagulating sedimentation: add saturated limewater and regulate pH value water outlet qualified discharge to neutrality, the coagulating sedimentation.
3. dye waste water treatment method according to claim 1 is characterized in that: the described physico-chemical pretreatment stage comprises the steps:
(1) interior electrolytic reaction: pending waste water from dyestuff is introduced the interior electrolytic reaction of interior electrolyzer generation of loading iron plane flower and coke according to a certain percentage remove a part of colourity and COD, described waste and old iron plane flower is to constitute macroscopical electrode with described coke by the body material of interior electrolytic reaction;
(2) coagulating sedimentation: the adding saturated limewater is regulated the pH value, coagulating sedimentation is removed most vitriol, colourity and COD.
4. according to claim 2 or 3 described dye waste water treatment methods, it is characterized in that: described iron plane flower and gac volume load than being 2: 1, described iron plane flower and coke volume load than being 2: 1, automatically ventilation recoil in the electrolytic reaction step makes gas-water ratio remain on 10: 1-20: 1 in described; Also add polymerize aluminum chloride and polyacrylamide in the coagulating sedimentation step in described physico-chemical pretreatment stage, the enhanced coagulation precipitation is removed most of colourity and COD in the waste water.
5. dye waste water treatment method according to claim 2, it is characterized in that: add before the interior electrolytic reaction the treatment stage of described advanced oxidation useless acid for adjusting pH value to 3-4 in case reach carry out in the optimal ph of electrolytic reaction, carry out described in electrolytic reaction 1-2 hour.
6. dye waste water treatment method according to claim 2, it is characterized in that: described oxygenant is 30% hydrogen peroxide, the hydrogen peroxide dosage is 1-2ml/L, reacts 2-3 hour, adds saturated limewater adjusting pH value and added the polyacrylamide precipitation again 1-2 hour to neutrality.
7. dye waste water treatment method according to claim 1 and 2, it is characterized in that: adopt upflow anaerobic sludge blanket process in described anaerobic treatment stage, and inoculation anaerobic grain sludge, carry out 4-6 month anaerobion domestication, and add engineering bacteria and eliminate in the waste water ammonia nitrogen and sulfide the influence of methanogen, chemistry, the biological respinse of a series of complexity takes place in the process anaerobion, removes colourity and also makes the anaerobism effluent quality help the degraded of aerobic microbiological more.
8. dye waste water treatment method according to claim 1 and 2, it is characterized in that: used carrier is urethane carrier that can fixation of microbe in described aerobic treatment, microbe inoculation is the similar waste water active sludge of pending waste water from dyestuff, and add engineering bacteria and carry out biochemical intensive treatment, the required dissolved oxygen of aerobic reaction is 3-5mg/L.
9. according to claim 2 or 3 described dye waste water treatment methods, it is characterized in that: carry out after the described physico-chemical pretreatment heating as required before the anaerobic treatment and regulating the pH value to follow-up anaerobic treatment stage required temperature and pH value, adjusting the pH value is that 6.5-7.0, temperature are 25 ℃-40 ℃, and according to carrying out anaerobic reaction behind the additional an amount of trace element of water quality situation.
10. according to the described dye waste water treatment method of one of claim 1 to 9, it is characterized in that: electrolytic reaction step and aerobic treatment stage are by the gas blower oxygen supply in described; The precipitating sludge that described coagulating sedimentation step, anaerobic treatment step produce is pressed into the mud cake outward transport.
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