CN103641274B - Technology for processing dye wastewater by combining advanced oxidation technology with biofilm process - Google Patents
Technology for processing dye wastewater by combining advanced oxidation technology with biofilm process Download PDFInfo
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- CN103641274B CN103641274B CN201310670975.0A CN201310670975A CN103641274B CN 103641274 B CN103641274 B CN 103641274B CN 201310670975 A CN201310670975 A CN 201310670975A CN 103641274 B CN103641274 B CN 103641274B
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- dye wastewater
- advanced oxidation
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Abstract
The invention discloses a technology for processing dye wastewater by combining an advanced oxidation technology with a biofilm process. The traditional technology is large in energy consumption, high in cost and troublesome in operation when used for processing the dye wastewater. The novel technology comprises the following steps of feeding the dye wastewater into an advanced oxidation pond, and adjusting the pH value to 3.5+/-0.2; adding H2O2 and Fe<2+>, stirring and reacting for 45 minutes, and then adjusting the pH value to 7.5+/-0.2; feeding the effluent of the advanced oxidation pond into a two-stage biofilm system to carry out biological aerobic degradation reaction; feeding the effluent of a second-stage biofilm reaction system into a settling pond, discharging a part of effluent after standing for 30 minutes, and back-flushing by using the other part of effluent, wherein the effluent indexes are as follows: the chemical oxygen demand (COD) is below 80mg/L and the chromaticity is smaller than 60. The novel technology has the advantages of being good in dye wastewater treatment effect, free of secondary pollution, low in energy consumption, low in water treatment cost, and capable of protecting the environment, thereby being beneficial to development of a dyeing enterprise.
Description
Technical field
the present invention relates to environmental protection technology, specifically a kind for the treatment of process of waste water from dyestuff.
Background technology
at present, dyestuff corporate boss will produce the products such as matching stain, neutral dye, mordant dyes and dyestuff intermediate.The waste water produced in DYE PRODUCTION process is high COD, high chroma, supersalinity and low BOD
5
the mother liquor of/COD and the mixture of washing water, cause great pollution to environment and water resources.COD is that chemical oxygen demand (COD) (Chemical Oxygen Demand) refers under certain conditions, adopts the oxidant content consumed during strong oxidizer process water sample; Be the index representing reducing substances quantity in water, chemical oxygen demand (COD) larger explanation water pollution is more serious.BOD is the oxygen requirement that biochemical oxygen demand (BOD) (Biochemical Oxygen Demand) refers to microbial decomposition.Usually with BOD
5
/ COD is greater than 0.25 as judging whether waste water is suitable for the index with Biochemical method.
waste water from dyestuff has following characteristics:
(1) with aromatic hydrocarbons and heterogeneous ring compound for parent and with colour developing group, easy oxidized generation quinoid compound produces stronger color development ability, brings great difficulty to dye wastewater treatment.
(2) organism good water solubility, complex structure and more than 97% containing benzene ring structure, be difficult to degraded; Along with the upgrading of dye product and the appearance of dyestuff new variety, the organic constitution in waste water is more complicated, brings difficulty to the process of waste water from dyestuff.
(3) in addition, normal containing sodium bicarbonate, oil in water emulsion, organic solvent and petroleum substance in waste water, waste water denseness is increased, and produces a large amount of foam, add intractability.
(4) in dye mother solution waste water COD up to 10000mg/L; Colourity is up to 12000 times; Salts contg is up to 9000mg/L; Wastewater biodegradability extreme difference (BOD
5
/ COD is 0.1); After mixing with washes, its concentration decreases, if but be directly discharged in water body, very big to environmental hazard.
prior art mainly contains following several method for the process of waste water from dyestuff:
(1) flocculent precipitation: the shortcoming of this method is, because waste water from dyestuff is water-soluble, flocculation sediment weak effect, and precipitating sludge intractability is large.
(2) absorption method:
a, acticarbon adsorb, and shortcoming is that regeneration is difficult, cost is too high.
, biological activity carbon adsorption, be subject to microorganism concn restriction, when microorganism concn is low, degradation effect is poor; Block gac duct during microorganism concn height, cause adsorption effect poor.
, micro-porous resin absorption, loading capacity is limited, can not meet the processing requirements of waste water from dyestuff, and adsorbent saturated after, easily form secondary pollution.
(3) electrochemical methods: as electrooxidation technology, photoxidation technology, microwave cooperating technology, electro-flotation and light electrolysis etc., although it is good that these methods have treatment effect, do not produce secondary pollution, the advantage that floor space is little, but it is large that its shortcoming is energy consumption, the waste water from dyestuff very easily fouling and clogging of process supersalinity, increases processing cost.
(4) biological treatment: biological treatment cost is low, but when supersalinity, because strain domestication effect is undesirable, affect degradation effect.
china Patent Publication No.: CN 101659500A, describe " a kind of dye waste water treatment system ", in this system, Aerobic Pond connects advanced oxidation process, although water outlet can touch the mark after process, but this method energy consumption is large, processing cost is high, and troublesome poeration.
china Patent Publication No.: CN101955303A, describe " a kind for the treatment of process of waste water from dyestuff ", researched and developed by this seminar, the method adopts " flocculation sediment-acidication-aerobic-remove inverse " main process, although water outlet can qualified discharge after process, in actual motion, find that this process operating management is complicated, energy consumption is higher.
dye wastewater process up to now remains an insoluble technical problem.
therefore a kind of process of invention high COD, high chroma, supersalinity, low BOD
5
the waste water from dyestuff of/COD is effective, cost is low, can not be formed the dye wastewater treatment novel method of secondary pollution for protection of the environment, to reduce cost of dye, improve dyestuff enterprise efficiency be the very important task of dyestuffs industries.
Summary of the invention
the object of this invention is to provide a kind of process high COD, high chroma, supersalinity, low BOD5/COD waste water from dyestuff effective, cost is low, can not form the dye wastewater treatment novel method of secondary pollution.
the object of the present invention is achieved like this:
a technique for high-level oxidation technology and biomembrance process combined treatment waste water from dyestuff, it comprises following 4 steps:
(1) advanced oxidation pond process:
1. waste water from dyestuff enters advanced oxidation pond;
2. in equalizing tank, add hydrochloric acid soln, adjust ph, to 3-4, is preferably 3.5 ± 0.2;
3. H is added
2
o
2
and Fe
2+
;
4. be 7-8 with sodium hydroxide solution by pH regulator after stirring reaction 45min, be preferably 7.5 ± 0.2;
5. effluent index COD is 430-480mg/L, is preferably 450mg/L;
(2) two-stage biological film process:
1. advanced oxidation pond water outlet (being controlled by under meter) enters first step biomembrane reaction system,
2. again from flowing to second stage biofilm system;
3. the liquid level of whole process is controlled by liquidometer, and hydraulic detention time is 10-14h, is preferably 12h;
(3) settling pond process:
1. the water outlet of second stage biomembrane reaction system enters into settling pond;
2. after static 20-40min, after being preferably 30min; Partial discharge, part is used for back flushing;
3. water outlet is COD is below 100mg/L, is preferably below 80mg/L;
4. colourity is less than 80, is preferably below 60mg/L;
(4) combined water and air backwash:
1. first water inlet is closed;
2. gas rushes 2-10min, is preferably 5min;
3. air water rushes 6-10 min, is preferably 8 min;
4. water rushes 12-15 min, is preferably 10 min;
5. backwashing period 100-150 h, is preferably 120h.
main points of the present invention are:
carry out technological transformation for existing dye wastewater treatment technique (flocculation sediment-acidication-aerobic-remove inverse), adopt H
2
o
2
/ Fe
2+
high-level oxidation technology and two-stage biological membranous system combination process.H
2
o
2
/ Fe
2+
high-level oxidation technology mainly utilizes Fe
2+
catalysis H
2
o
2
there is the OH that chain reaction produces, there is strong oxidation, to Persistent organic pollutants, there is good removal effect, the biodegradability of waste water can be improved simultaneously, follow-up biological respinse is laid the foundation.Two-stage biological membranous system is mainly theoretical based on pulling flow type high efficiency reactor, and a large biofilm system is decomposed two atom membranous system, and parallel-series is got up, and this will greatly increase biological treatment effect, guarantees that water quality reaching standard discharges and recycling.
the present invention compared with domestic and international existing similar technique, its creativeness be following some:
1, by H
2
o
2
/ Fe
2+
high-level oxidation technology and technology of biological membrane are organically coupled;
2, utilize technology of biological membrane to instead of traditional activated sludge process, eliminate sludge settling and return-flow system;
3, two-stage biological membranous system is together in series, serves good pulling flow type effect.
the difference of the present invention and domestic and international prior art is:
1, H is adopted
2
o
2
/ Fe
2+
high-level oxidation technology, and the O not adopting that energy consumption is high
3
/ UV and Fe/C light electrolysis high-level oxidation technology;
2, adopt technology of biological membrane, and do not adopt traditional activated sludge process;
3, the pulling flow type high efficiency reactor theory in chemical industry is incorporated in this novel process, substantially increases treatment effect.
advantage of the present invention is:
1, dye wastewater treatment is effective.
, energy expenditure is low, cost of water treatment is low.
, actually operating and operational management be convenient.
, protection water surrounding, be beneficial to dyeization enterprise development.
accompanying drawing illustrates: Fig. 1 is dye wastewater treatment schema of the present invention.
in figure: 1, advanced oxidation pond; 2, agitator; 3, pH meter; 4, under meter; 5: first step biofilm system; 6, second stage biofilm system; 7, liquidometer; 8, aerator; 9, settling pond; 10, back flushing water inlet; 11, back flushing water outlet.
Embodiment
specific embodiment of the invention measure is:
the Main Function in advanced oxidation pond 1 is the biodegradability removed part COD and improve waste water from dyestuff; Advanced oxidation pond 1 adds hydrochloric acid soln, and adjust pH is 3.5 ± 0.2, indicates with pH meter 3, is H
2
o
2
and Fe
2+
catalyzed reaction creates optimum operating mode; With agitator 2 stirring reaction 45min; Add sodium hydroxide solution again, adjust pH is 7.5 ± 0.2, with pH meter instruction, for follow-up biochemical reaction creates optimum environment.
the water outlet of advanced oxidation pond enters first step biofilm system 5 and second stage biofilm system 6, and its Main Function is the remaining COD of degraded, guarantees waste water energy qualified discharge and cycling and reutilization; During operation, hydraulic detention time is 12h; In this system, liquid level is controlled by liquidometer 7; Intrasystem oxygen carries out blast aeration by aerator 8.
the Main Function of settling pond 9 removes the microbial film come off.Biofilm system water outlet can be discharged after entering the static 30min of settling pond.
except backwashing period 120 h(burst accident), adopt combined water and air backwash method: first close water inlet; Then 5min is rushed by aerator gas; Aerator and settling pond water 10 carry out air water and rush 8 min; Settling pond water carries out water and rushes 10 min; Back flushing water outlet is discharged by pipeline 11.
this combination process is for high COD, high chroma, supersalinity, low BOD
5
the dye wastewater treatment of/COD, has good treatment effect, and water outlet reaches discharge and the reuse standard of national regulation, achieves waste water reclaiming and effects of energy saving and emission reduction, has obvious society, economy and environment benefit.
the present invention is adapted to produce the mother liquor of the products such as matching stain, neutral dye, mordant dyes and dyestuff intermediate and the composite wastewater process of washing water generation, as the sewage disposal of 80 kind dyestuffs such as production ACID BROWN A and acid blue 25, there is practicality widely.
Specific embodiment
below by specific embodiment, the present invention will be further described.
example 1:
get the composite wastewater 5L of mother liquor and the washing water generation of producing the products such as matching stain, neutral dye, mordant dyes and dyestuff intermediate, its COD is that 4600mg/L carries out pilot plant test.(1) pH is adjusted to be 3.46 with hydrochloric acid; (2) 30%H of 6.5mL is added
2
o
2
, 1.9 grams of FeSO
4
7H
2
45min is stirred under O, 200rpm rotating speed; (3) pH is adjusted to be 7.35 with sodium hydroxide; (4), in biofilm system, abundant aeration is used oxygen in water and is greater than 2.0mg/L; (5) biofilm system water outlet static 30min in settling pond, in supernatant liquor water outlet, COD is 76mg/L, and colourity is 52; (6) first water inlet is closed when the laggard row combined water and air backwash of operation 120 h is total to 23min(; Then gas rushes 5min; Air water rushes 8 min; Water rushes 10 min), during back flushing, the flow of the empty G&W of flow is 0.5 L/min.
example 2:
the pilot plant test of the present invention's " novel process of high-level oxidation technology and biomembrance process combined treatment waste water from dyestuff " carries out in Anhui dye chemical industry company limited, and the day process water yield is 100L.Comprehensive waste water from dyestuff water quality is: pH value 5.2, COD 4660 mg/L, salinity 5100 mg/L, colourity 4120 times (brown).Since pilot scale in June, 2012, achieve stable treatment effect, detailed process is as follows:
(1) pH is adjusted to be 3.5 ± 0.2 with hydrochloric acid;
(2) 30%H of 130mL is added
2
o
2
, 38 grams of FeSO
4
7H
2
45min is stirred under O, 200rpm rotating speed;
(3) pH is adjusted to be 7.35 ± 0.2 with sodium hydroxide;
(4), in biofilm system, abundant aeration (air flow quantity 1.5L/min) is used oxygen in water and is greater than 2.0mg/L;
(5) biofilm system water outlet static 30min in settling pond, in supernatant liquor water outlet, COD is 65 ± 8mg/L, and colourity is 46 ± 5;
(6) first water inlet is closed when the laggard row combined water and air backwash of operation 120 h is total to 23min(; Then gas rushes 5min; Air water rushes 8 min; Water rushes 10 min), during back flushing, the flow of the empty G&W of flow is 10 L/min.
as can be seen from above-mentioned example, no matter be pilot plant test or pilot plant test, the present invention for waste water from dyestuff, especially to high COD, high chroma, supersalinity, low BOD
5
the process of/COD " three high and one low " waste water from dyestuff, has good treatment effect.
above-described embodiment is only preference of the present invention, is not used for limiting the present invention, all within principle of the present invention, and any equivalent alternative, the modifications and variations done, all within protection scope of the present invention.
Claims (5)
1. a technique for high-level oxidation technology and biomembrance process combined treatment waste water from dyestuff, is characterized in that, it comprises following 4 steps:
(1) advanced oxidation pond process:
1. waste water from dyestuff enters advanced oxidation pond;
2. in equalizing tank, add hydrochloric acid soln, adjust ph is to 3-4;
3. H is added
2o
2and Fe
2+;
4. be 7-8 with sodium hydroxide solution by pH regulator after stirring reaction 45min;
5. effluent index COD is 430-480mg/L;
(2) two-stage biological film process:
1. the water outlet of advanced oxidation pond controls to enter first step biomembrane reaction system by under meter;
2. again from flowing to second stage biofilm system;
3. the liquid level of whole process is controlled by liquidometer, and hydraulic detention time is 10-14h;
(3) settling pond process:
1. the water outlet of second stage biomembrane reaction system enters into settling pond;
2. static 20-40min rear section discharge, part is used for back flushing;
3. water outlet is COD is below 100mg/L;
4. colourity is less than 80;
(4) combined water and air backwash:
1. first water inlet is closed;
2. gas rushes 2-10min;
3. air water rushes 6-10 min;
4. water rushes 12-15 min;
5. backwashing period 100-150 h.
2. the technique of dye wastewater treatment according to claim 1, is characterized in that, in the treating processes of advanced oxidation pond:
(1) hydrochloric acid described in by pH regulator to 3.5 ± 0.2;
(2) sodium hydroxide described in by pH regulator to 7.5 ± 0.2;
(3) the effluent index COD described in is 450mg/L.
3. the technique of dye wastewater treatment according to claim 1, is characterized in that, in two-stage biological film treating processes, hydraulic detention time is 12h.
4. the technique of dye wastewater treatment according to claim 1, is characterized in that, in settling pond treating processes:
(1) partial discharge described in is in the discharge of static 30min rear section;
(2) the water outlet COD index described in is below 80mg/L;
(3) effluent color dilution described in is less than 60.
5. the technique of dye wastewater treatment according to claim 1, is characterized in that, in combined water and air backwash process:
(1) the gas time of rushing described in is 5min;
(2) the air water time of rushing described in is 8 min;
(3) the water time of rushing described in is 10 min;
(4) backwashing period described in is 120h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310670975.0A CN103641274B (en) | 2013-12-12 | 2013-12-12 | Technology for processing dye wastewater by combining advanced oxidation technology with biofilm process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310670975.0A CN103641274B (en) | 2013-12-12 | 2013-12-12 | Technology for processing dye wastewater by combining advanced oxidation technology with biofilm process |
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| CN103641274B true CN103641274B (en) | 2015-03-25 |
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| CN104291506B (en) * | 2014-09-18 | 2016-01-20 | 中国海洋石油总公司 | A kind of method of microwave reinforced light electrolysis combination oxide treatment rubber ingredients waste water |
| CN104860470A (en) * | 2015-04-28 | 2015-08-26 | 山东先达农化股份有限公司 | Acrolein wastewater treatment method and device |
| CN106277553A (en) * | 2015-05-27 | 2017-01-04 | 麦王环境技术股份有限公司 | The processing method of the dense water of reverse osmosis (RO) and equipment |
| CN105502816A (en) * | 2015-12-10 | 2016-04-20 | 苏州国环环境检测有限公司 | Method for degrading organic substances in sewage |
| CN110563116A (en) * | 2019-09-09 | 2019-12-13 | 安徽科技学院 | Method for degrading azo dye gold orange II solution by catalyzing persulfate through aluminum alloy pickling waste liquid |
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| JP2007330914A (en) * | 2006-06-16 | 2007-12-27 | Japan Organo Co Ltd | Method and apparatus for making oxidizable atmosphere water, water treatment method and water treatment apparatus |
| CN102358650B (en) * | 2011-09-22 | 2012-12-26 | 北京科泰兴达高新技术有限公司 | Advanced purification and recycling method and device of nondegradable organic industrial wastewater |
| KR101400332B1 (en) * | 2012-03-29 | 2014-05-27 | 현대제철 주식회사 | Creation apparatus of iron salt and removal apparatus of polluted matter having the same |
| CN103145274B (en) * | 2013-03-15 | 2014-06-25 | 中北大学 | Method and device for treating wastewater by advanced oxidation process |
| CN103359878B (en) * | 2013-07-12 | 2014-09-10 | 华南理工大学 | Treatment method for realizing zero emission of printing and dyeing wastewater |
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