CN100591632C - Advanced treatment method and device for dyeing waste water by ozone iron zinc catalysis - Google Patents

Advanced treatment method and device for dyeing waste water by ozone iron zinc catalysis Download PDF

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Publication number
CN100591632C
CN100591632C CN200810063462A CN200810063462A CN100591632C CN 100591632 C CN100591632 C CN 100591632C CN 200810063462 A CN200810063462 A CN 200810063462A CN 200810063462 A CN200810063462 A CN 200810063462A CN 100591632 C CN100591632 C CN 100591632C
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waste water
water
die cavity
catalytic
ozone
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CN101337754A (en
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董滨
杨青淼
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ZHEJIANG YONGFENG ENVIRONMENTAL ENGINEERING TECHNOLOGY CO., LTD.
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石永丰
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Abstract

The invention relates to an advanced treatment method and a device of dyeing wastewater ozone catalytic iron zinc. After adopting the preparation step, the catalytic packing material fabricating step,the catalytic bed fabricating step, the step of filling ozone to wastewater, the wastewater catalytic step, the wastewater biodegradation step and the processing water leading step, the method has stable treatment effect, and has stronger decomposition capacity to heterocyclic organisms resided in dyeing wastewater; and qualified water formed after passing through a water outlet pipe is led out of a disposal basin body. The device comprises a disposal basin body; catalytic packing materials are filled in the grid body of a first mould cavity of the disposal basin body; microorganisms are filled in the grid body of a second mould cavity, and an aeration biological filter tank is formed in the second mould cavity; the first mould cavity positioned at the lower part of the grid body is a water inlet cavity; and a water inlet pipe and an air outlet of an ozonizer are connected with the water inlet cavity simultaneously; a circulating water pump is arranged between a first water outlet cavity and the water inlet cavity; and a water outlet pipe is connected with a second water outlet cavity, and further provided with an aerator. The device has the advantages of strong operability and high automation during the running process.

Description

A kind of dyeing waste water by ozone iron zinc catalysis deep treatment method and device
Technical field
The present invention relates to the technical field of dyeing waste water advanced treatment and middle water reuse, particularly a kind of dyeing waste water by ozone iron zinc catalysis deep treatment method and device, and the device of realizing this method.
Background technology
The dyeing waste water amount is big, and pollution load is heavy, and dyeing waste water is through after the conventional second-stage treatment, and the water outlet COD that water outlet can reach " integrated wastewater discharge standard " GB8978-1996 regulation is lower than the emission request of 100mg/L.Along with the growing tension of water resources, dyeing waste water further carries out advanced treatment through after the second-stage treatment, is back to after the water water quality standard in the printing and dyeing industry production in reaching, and will have huge economy and society benefit.But dyeing waste water is easy to biodegradable organism approach exhaustion through after the second-stage treatment in the waste water, mainly be the organism of macromole difficult degradation among the residual COD, has caused very big difficulty for further advanced treatment.Practice shows, adopts general biological process, and is not good for the residual COD treatment effect of this part as activated sludge process or biomembrance process, is difficult to reach the required middle water water quality requirement of enterprise, and simple chemical agent flocculence also is difficult to play positive effect.Adopt chemical oxidization method, as Fenton reagent etc., can play the oxidation removal effect to residual difficult degradation COD, but running cost is too high, enterprise can't bear.
The main method patent of dyeing waste water advanced treatment and middle water reuse has at present:
1, be 200710008643.0 Chinese patent application patent " a kind of treatment method of printing and dying wastewater " (notification number: CN101041532A): provide a kind of and combine with dyeing waste water conventional processing technology, the advanced treatment method for printing and dyeing wastewater of water reuse during water outlet reaches as number of patent application based on membrane technique based on membrane technique.The concrete implementation step of this method is: comprehensive wastewater is regulated pH and COD value, comprehensive wastewater is pumped into flocculation jar to add a flocculation agent and pumps into the flocculating settling container and get clear liquor, clear liquor pumps into membrane bioreactor to carry out biochemical treatment and gets dialyzate, dialyzate pumps into the reverse osmosis isolation system to carry out reverse osmosis isolation and gets the reuse of reverse osmosis dialyzate, concentrated solution flows into the oxidation adsorption tank and handles, and concentrated solution passes back into the flocculating settling treatment process to carry out the secondary flocculating settling and handle and reach the secondary discharge standard discharging.The discharging of reverse osmosis dialyzate eligible, the failure adds the ClO2 oxidation and regulates pH through the charcoal absorption processing and with alkali lye, precipitates in storagetank.Reverse osmosis waste water discharges after the conformance with standard after testing.
2, as number of patent application be 200710067593.3 Chinese patent application patent " the polyester piece good dyeing and finishing wastewater is handled and recycling method " (notification number: CN101041538A): present method with the polyester piece good dyeing and finishing wastewater by ternary compound inorganic high molecular flocculant and the common flocculation treatment of natural polymer composite flocculation agent, pass through filtering technique again, and in conjunction with biological treatment and ozone sterilization processing, the middle water that obtains mixes with clear water, selectively is back to the polyester piece good dyeing and finishing course of processing.This method can be removed colourity and COD value in the dyeing waste water fast, and running cost is lower, and the reuse ratio is higher.
3, as number of patent application be 03139857.X Chinese patent application patent " dyeing waste water deep purifying reclamation set and method " (notification number: CN1569694A): present method includes except that equalizing tank, anaerobic pond, aerobic aeration pond and settling tank, also have additional the ClO2 oxidation pond, the dispensing coagulation basin, biological activated carbon filter and fiber ball filter.The treatment process that adopts biochemistry and materialization to combine, wherein remove most COD and pollutents such as N, P by biochemical treatment, utilize the ClO2 oxidation, decompose remaining hardly degraded organic substance and dyestuff, filtration through offer medicine coagulating sedimentation and biological activated carbon, fibrous nodules further purifies water outlet again, makes dyeing waste water reach technology reuse water quality requirement.Its purification efficiency height, stable effluent quality, construction investment is few, working cost is low, be easy to apply.
4, be that (notification number: CN1765779A): present method is to be primarily aimed at the system process that desized wastewater, alkali decrement waste water and dyeing waste-water recycle for 200510060615.4 Chinese patent application patent " printing and dyeing wastewater recovery and disposal method " as number of patent application, it is handled the waste water that reclaims and can use in dyeing process, do not influence the dyeing and printing products quality, the rate of recovery is higher, and invests less.Basic skills is: desized wastewater, alkali decrement waste water are carried out the acid out pre-treatment respectively, the slurry that recovery is separated out carries out the A/O biochemical treatment with dyeing waste-water then, again after the ozone catalytic advanced treatment, most of water is back to dyeing, realizes the reuse of dyeing and printing sewage.
Summary of the invention
Technical problem to be solved by this invention is the present situation at prior art, provides a kind of with low cost, reliable, simple operation, treatment effect to reach the dyeing waste water by ozone iron zinc catalysis deep treatment method and the device of convenient management well.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: a kind of dyeing waste water by ozone iron zinc catalysis deep treatment method and device, comprise preparation step: prepare the treating pond body that an inside is divided into first die cavity and second die cavity, this treatment process also includes following steps:
Make the catalytic filler step: adopt iron material or Zinc material starting material, and these starting material are immersed in saturated CuSO as catalytic filler 4In the solution, soak time can plate the layer of copper material on raw-material surface like this, and be made into catalytic filler about two hours;
Make the catalytic bed step: the catalytic filler that the surface has been plated copper product is packed in first die cavity for the treatment of pond body, and forms catalytic bed in this first die cavity for the treatment of pond body; Its filling density of the catalytic filler that this catalytic bed is filled is controlled at 0.6 ton/m 3To 1.0 tons/m 3Between;
Waste water fills the ozone step: the intake antrum at the treating pond body connects ozonizer, this ozonizer air outlet is set up in parallel mutually with water inlet pipe, when waste water the time from water inlet pipe input intake antrum, the ozone that ozonizer produces also is input in the intake antrum simultaneously, and forms the gas-liquid mixture of ozone and waste water in intake antrum; The input concentration of general ozone is controlled between the 50mg/L to 150mg/L;
The waste water catalytic step: the gas-liquid mixture of ozone and waste water is flowed through after the catalytic bed, a series of catalyzed chemical reactions can take place in the composition in the waste water, waste water after the catalysis its former organic molecular structure that remains be damaged, an organic part is decomposed into small molecules and is easy to biodegradable organism, and organic another part is an inorganic carbon by ozone oxidation directly;
The wastewater biological degradation step: second die cavity for the treatment of pond body is filled with the BAF of microorganism in being; Waste water after institute's catalysis is gone in the BAF of this second die cavity by the first die cavity overflow for the treatment of pond body; The waste water of the microorganism of this BAF after to catalysis is done further biological degradation, and with in the waste water residual partial organic substances be degraded to inorganic carbon, so far the waste water of being imported becomes the qualified water that COD is lower than 30mg/L after catalysis, oxidation and biological degradation;
Treating water output step: it is external that formed qualified water is output in treating pond through rising pipe.
The measure of taking also comprises:
In the above-mentioned waste water catalytic step, the copper facing generation galvanic cell reaction that iron material in the above-mentioned catalytic filler or Zinc material are surperficial with it, under the katalysis of copper product, organism in the waste water will become electron acceptor(EA), electron-withdrawing group in the larger molecular organics of part heterocyclic, azo class adds the electronics reaction, thereby make the complicated molecule structure take place to destroy and variation, be split into and be easy to follow-up biodegradable small molecules.
In the above-mentioned waste water catalytic step, dissolving to a certain degree takes place in the gas-liquid mixture of above-mentioned ozone and waste water and the iron material in the catalytic filler or Zinc material, institute's dissolved iron ion or zine ion play throwing out to organism, help the removal effect of larger molecular organics.
Above-mentioned waste water fills that ozone forms the OH molecular chain in the ozone step in waste water water, and this OH molecular chain has stronger oxygenizement; And this OH molecular chain combines with institute's dissolved iron ion or zine ion in the waste water catalytic step, directly organism produces strong oxidation in the waste water to having, make that larger molecular organics is decomposed into small organic molecule in the waste water, the part small organic molecule can direct oxidation be CO in the waste water 2And H 2O.
The copper facing on above-mentioned catalytic filler surface in wastewater treatment process not only as the negative electrode of Cu-Fe/Zn galvanic cell, and at OH, Fe → Fe 2+→ Fe 3+, Zn → Zn 2+, O 3, in the complex reaction system formed of organism, play the effect of important catalyzed reaction, can add the fast response electronic transfer process greatly, heterocyclic residual in the dyeing waste water, azo type organic are effectively destroyed and decompose, guarantee the removal effect of following adopted aeration and biological degraded.
A kind of dyeing waste water by ozone iron zinc catalysis advanced treatment apparatus, comprise the treating pond body, this treating pond body is divided into two die cavities, it is respectively first die cavity and second die cavity, all be fixed with the grid body of upper and lower settings in first die cavity and second die cavity, be filled with catalytic filler in the grid body of first die cavity, be filled with microorganism in the grid body of second die cavity, and in second die cavity, form BAF, the below that first die cavity is positioned at the grid body is an intake antrum, and this intake antrum is connected with the air outlet of water inlet pipe and ozonizer simultaneously; The top that first die cavity is positioned at the grid body is first water chamber, is equipped with water circulating pump between this first water chamber and the intake antrum; The below that second die cavity is positioned at BAF is second water chamber, and this second water chamber is connected with rising pipe, and also is equipped with aerator in this second water chamber.
First kind of technical scheme of above-mentioned catalytic filler is: above-mentioned catalytic filler is the iron-based filler; Be provided with central dividing plate between first die cavity and second die cavity, this central dividing plate top is shaped on the overflow edge.
First kind of technical scheme of above-mentioned catalytic filler is: above-mentioned catalytic filler is the zinc-base filler; Be provided with central dividing plate between first die cavity and second die cavity, this central dividing plate top is shaped on the overflow edge.
First kind of technical scheme of above-mentioned catalytic filler is: above-mentioned catalytic filler 11a is the mixture of iron-based filler and zinc-base filler; Be provided with central dividing plate 12 between the first die cavity 9a and the second die cavity 9b, these central dividing plate 12 tops are shaped on overflow edge 12a.
Above-mentioned iron-based filler is electroplate with one deck copper product at least in appearance, and correspondingly, above-mentioned zinc-base filler also is electroplate with one deck copper product at least in appearance; The filling density range of above-mentioned catalytic filler 11a is 0.6 ton every cube to 1 ton every cube.
Compared with prior art, all be fixed with the grid body of upper and lower settings in the present invention's first die cavity and second die cavity, be filled with catalytic filler in the grid body of first die cavity, be filled with microorganism in the grid body of second die cavity, and in second die cavity, form BAF, the below that first die cavity is positioned at the grid body is an intake antrum, and this intake antrum is connected with the air outlet of water inlet pipe and oxygengenerator difficult to understand simultaneously; The top that first die cavity is positioned at the grid body is first water chamber, is equipped with water circulating pump between this first water chamber and the intake antrum; The below that second die cavity is positioned at BAF is second water chamber, and this second water chamber is connected with rising pipe, and also is equipped with aerator in this second water chamber; The operational process of device is workable, the level of automation height, and convenient management, running cost is lower; After adopting preparation step, making catalytic filler step, making catalytic bed step, waste water to fill ozone step, waste water catalytic step, wastewater biological degradation step, treating water output step, treatment effect is stable, and heterocyclic organism residual in the dyeing waste water is had stronger capacity of decomposition; Combine with follow-up BAF bioremediation, reach integrated design, reduce investment outlay and take up an area of; Ozone catalytic iron/zinc+BAF method treatment effect is stable, can directly reach middle water quality standard; It is external that the qualified water that forms is output in treating pond through rising pipe.
Description of drawings
Fig. 1 is the synoptic diagram of the embodiment of the invention.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Embodiment as shown in Figure 1, figure grade explanation: water inlet pipe 1, catalytic bed 11, catalytic filler 11a, grid body 11b, central dividing plate 12, overflow edge 12a, ozonizer 2, air outlet 2a, water circulating pump 3, BAF 6, aerator 7, rising pipe 8, treating pond body 9, the first die cavity 9a, the second die cavity 9b, intake antrum 91, the first water chambers 92, the second water chambers 93.
The embodiment of the invention, a kind of dyeing waste water by ozone iron zinc catalysis deep treatment method and device comprise preparation step: prepare the treating pond body 9 that an inside is divided into the first die cavity 9a and the second die cavity 9b, this treatment process also includes following steps:
Make the catalytic filler step: adopt iron material or Zinc material starting material, and these starting material are immersed in saturated CuSO as catalytic filler 11a 4In the solution, soak time can plate the layer of copper material on raw-material surface like this about two hours, and is made into catalytic filler 11a;
Make the catalytic bed step: the catalytic filler 11a that the surface has been plated copper product is packed in the first die cavity 9a for the treatment of pond body 9, and forms catalytic bed 11 in treating pond body 9 this first die cavity 9a; Its filling density of the catalytic filler 11a that this catalytic bed 11 is filled is controlled at 0.6 ton/m 3To 1.0 tons/m 3Between;
Waste water fills the ozone step: the intake antrum 91 at treating pond body 9 connects ozonizer 2, this ozonizer 2 air outlet 2a are set up in parallel mutually with water inlet pipe 1, when waste water the time from water inlet pipe 1 input intake antrum 91, the ozone that ozonizer 2 produces also is input in the intake antrum 91 simultaneously, and forms the gas-liquid mixture of ozone and waste water in intake antrum 91; The input concentration of ozone is controlled between the 50mg/L to 150mg/L;
The waste water catalytic step: the gas-liquid mixture of described ozone and waste water is flowed through after the catalytic bed 11, a series of catalyzed chemical reactions can take place in the composition in the waste water, waste water after the catalysis its former organic molecular structure that remains be damaged, an organic part is decomposed into small molecules and is easy to biodegradable organism, and organic another part is an inorganic carbon by ozone oxidation directly;
The wastewater biological degradation step: the second die cavity 9b for the treatment of pond body 9 is filled with the BAF 6 of microorganism in being; Waste water after institute's catalysis is gone in the BAF 6 of this second die cavity 9b by the first die cavity 9a overflow for the treatment of pond body 9; The waste water of the microorganism of this BAF 6 after to catalysis is done further biological degradation, and with in the waste water residual partial organic substances be degraded to inorganic carbon, so far the waste water of being imported becomes the qualified water that COD is lower than 30mg/L after catalysis, oxidation and biological degradation;
Treating water output step: formed qualified water is outside rising pipe 8 is output in treating pond body 9.
Present embodiment is achieved in that
In the waste water catalytic step, the copper facing generation galvanic cell reaction that iron material among the described catalytic filler 11a or Zinc material are surperficial with it, under the katalysis of copper product, organism in the waste water will become electron acceptor(EA), electron-withdrawing group in the larger molecular organics of part heterocyclic, azo class adds the electronics reaction, thereby make the complicated molecule structure take place to destroy and variation, be split into and be easy to follow-up biodegradable small molecules.
In the waste water catalytic step, dissolving to a certain degree takes place in iron material among the gas-liquid mixture of described ozone and waste water and the catalytic filler 11a or Zinc material, institute's dissolved iron ion or zine ion play throwing out to organism, help the removal effect of larger molecular organics.
Waste water fills that ozone forms the OH molecular chain in the ozone step in waste water water, and this OH molecular chain has stronger oxygenizement; And this OH molecular chain combines with institute's dissolved iron ion or zine ion in the waste water catalytic step, directly organism produces strong oxidation in the waste water to having, make that larger molecular organics is decomposed into small organic molecule in the waste water, the part small organic molecule can direct oxidation be CO in the waste water 2And H 2O.
The copper facing on catalytic filler 11a surface in wastewater treatment process not only as the negative electrode of Cu-Fe/Zn galvanic cell, and at OH, Fe → Fe 2+→ Fe 3+, Zn → Zn 2+, O 3, in the complex reaction system formed of organism, play the effect of important catalyzed reaction, can add the fast response electronic transfer process greatly, heterocyclic residual in the dyeing waste water, azo type organic are effectively destroyed and decompose, guarantee the removal effect of following adopted aeration and biological degraded.
A kind of dyeing waste water by ozone iron zinc catalysis advanced treatment apparatus, comprise treating pond body 9, this treating pond body 9 is divided into two die cavities, it is respectively the first die cavity 9a and the second die cavity 9b, all be fixed with the grid body 11b of upper and lower settings in the first die cavity 9a and the second die cavity 9b, be filled with catalytic filler 11a in the grid body 11b of the first die cavity 9a, be filled with microorganism in the grid body 11b of the second die cavity 9b, and in the second die cavity 9b, form BAF 6, the below that the first die cavity 9a is positioned at grid body 11b is an intake antrum 91, and this intake antrum 91 is connected with the air outlet 2a of water inlet pipe 1 and ozonizer 2 simultaneously; The top that the first die cavity 9a is positioned at grid body 11b is first water chamber 92, is equipped with water circulating pump 3 between this first water chamber 92 and the intake antrum 91; The below that the second die cavity 9b is positioned at BAF 6 is second water chamber 93, and this second water chamber 93 is connected with rising pipe 8, and also is equipped with aerator 7 in this second water chamber 93.
First kind of embodiment of catalytic filler is: catalytic filler 11a is the iron-based filler; Be provided with central dividing plate 12 between the first die cavity 9a and the second die cavity 9b, these central dividing plate 12 tops are shaped on overflow edge 12a.
Second kind of embodiment of catalytic filler is: catalytic filler 11a is the zinc-base filler; Be provided with central dividing plate 12 between the first die cavity 9a and the second die cavity 9b, these central dividing plate 12 tops are shaped on overflow edge 12a.
The third embodiment of catalytic filler is: catalytic filler 11a is the mixture of iron-based filler and zinc-base filler; Be provided with central dividing plate 12 between the first die cavity 9a and the second die cavity 9b, these central dividing plate 12 tops are shaped on overflow edge 12a.
The iron-based filler is electroplate with one deck copper product at least in appearance, and correspondingly, the zinc-base filler also is electroplate with one deck copper product at least in appearance; The filling density range of described catalytic filler 11a is 0.6 ton/m 3To 1.0 tons/m 3
The principle of work of the embodiment of the invention is as follows:
Dyeing waste water is through after the conventional secondary biochemical treatment, and generally its COD is controlled in 100mg/L to the 200mg/L scope, and this type of waste water can adopt present technique to carry out advanced treatment.With iron or zinc-base material, also can adopt wood shavings or sheet material earlier, place saturated CuSO 4About 2 hours, iron or zinc-base material surface can plate the layer of copper material in the solution, and form catalytic filler 11a.The catalytic filler 11a that plated copper powder is made catalytic bed 11, and the filling density of catalytic filler 11a is controlled at 0.6 ton/m in the catalytic bed 11 3To 1.0 tons/m 3
Be equipped with ozonizer 2, in the operational process, add a certain amount of ozone in waste water, general concentration is controlled at 50mg/L to 150mg/L.When the waste water that is dissolved with ozone is flowed through catalytic bed 11, form ozone catalytic iron/zinc bed, a series of catalyzed chemical reactions can take place, heterocyclic macromole hardly degraded organic substances such as anthraquinone residual in the dyeing waste water are destroyed and Degradation.This device implementation method is simple, obvious processing effect.
At first, iron or zinc-base material can react with the copper generation galvanic cell that its surface is coated with, dissolving to a certain degree takes place in iron or zinc-base material, be accompanied by the transfer process of electronics, under the katalysis of copper, organism will become electron acceptor(EA), and the electron-withdrawing group in the larger molecular organics of a part of heterocyclic, azo class adds the electronics reaction, thereby make the complicated molecule structure take place to destroy and variation, be split into and be easy to follow-up biodegradable small molecules.And dissolved iron ion or zine ion will play throwing out to organism again, also help the removal effect of larger molecular organics.
Secondly, ozone forms the OH molecular chain and has stronger oxygenizement in water, have Fe in water 2+/ Zn 2+Situation under, can form the oxidising process that is similar to Fenton reagent, it is stronger in the water oxygen voltinism, can be directly organism be produced strong oxidation, make larger molecular organics be decomposed into small organic molecule, the direct oxidation of part small organic molecule is CO 2And H 2O.
In addition, copper in this system not only as the negative electrode of Cu-Fe/Zn galvanic cell, and at OH, Fe → Fe 2+→ Fe 3+, Zn → Zn 2+, O 3, in the complex reaction system formed of organism, play the effect of important catalyzed reaction, can add the fast response electronic transfer process greatly, heterocyclic residual in the dyeing waste water, azo type organic are effectively destroyed and decompose, guarantee the removal effect of following adopted aeration and biological filter method.
The present invention is intended to develop a kind of with low cost, effective advanced treatment method for printing and dyeing wastewater, ozone catalytic iron/zinc catalytic bed has been proposed, effectively destroy heterocyclic, azo class hardly degraded organic substance molecular structure in the dyeing waste water, improve biodegradability, it is follow-up or connect biological treatments such as BAF and make water outlet reach water water quality standard in the printing and dyeing enterprise, break through the technical bottleneck in dyeing waste water advanced treatment and middle water reuse field, technical show-how and popularization are carried out in water reuse field in dyeing waste water.
The invention has the advantages that: operational process is workable, the level of automation height, and convenient management, running cost is lower; Adopt the method for ozone catalytic iron/zinc, treatment effect is stable, and heterocyclic organism residual in the dyeing waste water is had stronger capacity of decomposition; Combine with follow-up BAF bioremediation, reach integrated design, reduce investment outlay and take up an area of; Ozone catalytic iron/zinc+BAF method treatment effect is stable, can directly reach middle water quality standard.
Most preferred embodiment of the present invention is illustrated, and various variations or the remodeling made by those of ordinary skills can not depart from the scope of the present invention.

Claims (7)

1, a kind of dyeing waste water by ozone iron zinc catalysis deep treatment method comprises preparation step: prepare the treating pond body (9) that an inside is divided into first die cavity (9a) and second die cavity (9b), it is characterized in that: this treatment process also includes following steps:
Make the catalytic filler step: adopt iron material or Zinc material starting material, and these starting material are immersed in saturated CuSO as catalytic filler (11a) 4In the solution, soak time can plate the layer of copper material on raw-material surface like this about two hours, and is made into catalytic filler (11a);
Make the catalytic bed step: the described catalytic filler (11a) that the surface has been plated copper product is packed in first die cavity (9a) for the treatment of pond body (9), and forms catalytic bed (11) in this first die cavity (9a) for the treatment of pond body (9); Its filling density of the catalytic filler (11a) that this catalytic bed (11) is filled is controlled at 0.6 ton/m 3To 1.0 tons/m 3Between;
Waste water fills the ozone step: the intake antrum (91) in treating pond body (9) connects ozonizer (2), this ozonizer (2) air outlet (2a) is set up in parallel mutually with water inlet pipe (1), when waste water the time from water inlet pipe (1) input intake antrum (91), the ozone that ozonizer (2) produces also is input in the intake antrum (91) simultaneously, and forms the gas-liquid mixture of ozone and waste water in intake antrum (91); The input concentration of ozone is controlled between the 50mg/L to 150mg/L;
The waste water catalytic step: the gas-liquid mixture of described ozone and waste water is flowed through after the catalytic bed (11), a series of catalyzed chemical reactions can take place in the composition in the waste water, waste water after the catalysis its former organic molecular structure that remains be damaged, an organic part is decomposed into small molecules and is easy to biodegradable organism, and organic another part is an inorganic carbon by ozone oxidation directly;
The wastewater biological degradation step: second die cavity (9b) of described treating pond body (9) is filled with the BAF (6) of microorganism in being; Waste water after institute's catalysis is gone in the BAF (6) of this second die cavity (9b) by first die cavity (9a) overflow for the treatment of pond body (9); The waste water of the microorganism of this BAF (6) after to catalysis is done further biological degradation, and with in the waste water residual partial organic substances be degraded to inorganic carbon, so far the waste water of being imported becomes the qualified water that COD is lower than 30mg/L after catalysis, oxidation and biological degradation;
Treating water output step: formed qualified water is outside rising pipe (8) is output in treating pond body (9).
2, a kind of dyeing waste water by ozone iron zinc catalysis deep treatment method according to claim 1, it is characterized in that: in the described waste water catalytic step, the copper facing generation galvanic cell reaction that iron material in the catalytic filler (11a) or Zinc material are surperficial with it, under the katalysis of copper product, organism in the waste water will become electron acceptor(EA), electron-withdrawing group in the larger molecular organics of part heterocyclic, azo class adds the electronics reaction, thereby make the complicated molecule structure take place to destroy and variation, be split into and be easy to follow-up biodegradable small molecules.
3, a kind of dyeing waste water by ozone iron zinc catalysis deep treatment method according to claim 2, it is characterized in that: in the described waste water catalytic step, dissolving to a certain degree takes place in iron material in the gas-liquid mixture of described ozone and waste water and the catalytic filler (11a) or Zinc material, institute's dissolved iron ion or zine ion play throwing out to organism, help the removal effect of larger molecular organics.
4, a kind of dyeing waste water by ozone iron zinc catalysis deep treatment method according to claim 3 is characterized in that: described waste water fills that ozone forms the OH molecular chain in the ozone step in waste water water, and this OH molecular chain has stronger oxygenizement; And this OH molecular chain combines with institute's dissolved iron ion or zine ion in the waste water catalytic step, directly organism produces strong oxidation in the waste water to having, make that larger molecular organics is decomposed into small organic molecule in the waste water, the part small organic molecule can direct oxidation be CO in the waste water 2And H 2O.
5, a kind of dyeing waste water by ozone iron zinc catalysis deep treatment method according to claim 4, it is characterized in that: the copper facing on described catalytic filler (11a) surface in wastewater treatment process not only as the negative electrode of Cu-Fe/Zn galvanic cell, and at OH, Fe → Fe 2+→ Fe 3+, Zn → Zn 2+, O 3, in the complex reaction system formed of organism, play the effect of important catalyzed reaction, can add the fast response electronic transfer process greatly, heterocyclic residual in the dyeing waste water, azo type organic are effectively destroyed and decompose, guarantee the removal effect of following adopted aeration and biological degraded.
6, a kind of dyeing waste water by ozone iron zinc catalysis advanced treatment apparatus, comprise treating pond body (9), this treating pond body (9) is divided into two die cavities, it is respectively first die cavity (9a) and second die cavity (9b), all be fixed with the grid body (11b) of upper and lower settings in described first die cavity (9a) and second die cavity (9b), it is characterized in that: be filled with catalytic filler (11a) in the grid body (11b) of described first die cavity (9a), be filled with microorganism in the grid body (11b) of described second die cavity (9b), and in second die cavity (9b), form BAF (6), the below that described first die cavity (9a) is positioned at grid body (11b) is intake antrum (91), and this intake antrum (91) is connected with the air outlet (2a) of water inlet pipe (1) and ozonizer (2) simultaneously; The top that described first die cavity (9a) is positioned at grid body (11b) is first water chamber (92), is equipped with water circulating pump (3) between this first water chamber (92) and the intake antrum (91); The below that described second die cavity (9b) is positioned at BAF (6) is second water chamber (93), and this second water chamber (93) is connected with rising pipe (8), and also is equipped with aerator (7) in this second water chamber (93); Described catalytic filler (11a) is iron-based filler, zinc-base filler or the mixture of the two, and described iron-based filler is electroplate with one deck copper product at least in appearance, and described zinc-base filler also is electroplate with one deck copper product at least in appearance; Be provided with central dividing plate (12) between described first die cavity (9a) and second die cavity (9b), this central dividing plate (12) top is shaped on overflow edge (12a).
7, according to the described a kind of dyeing waste water by ozone iron zinc catalysis advanced treatment apparatus of claim 6 claim, it is characterized in that: the filling density range of described catalytic filler (11a) is 0.6 ton/m 3To 1.0 tons/m 3
CN200810063462A 2008-08-07 2008-08-07 Advanced treatment method and device for dyeing waste water by ozone iron zinc catalysis Expired - Fee Related CN100591632C (en)

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CN101700927B (en) * 2009-11-30 2012-01-04 哈尔滨工业大学 Method for processing water supply depth by united use of metallic zinc and ozone
CN102417258B (en) * 2011-11-11 2013-08-28 华南理工大学 Device and method for treating pulping wastewater by catalyst and ozone
CN102849824B (en) * 2012-03-22 2014-06-04 武汉科梦环境工程有限公司 Iron-based copper for treating organic sewage and sewage treatment method
CN103318990B (en) * 2013-07-04 2014-10-08 哈尔滨工业大学 Method for removing organic pollutants in water through electrochemical cathode catalytic ozonation
CN103991989A (en) * 2014-06-11 2014-08-20 高前松 Method for treating organic wastewater
CN104628187A (en) * 2015-02-01 2015-05-20 中南民族大学 Vertical-flow multi-stage gradient catalytic ozonation and filtering integrated tank
CN105236697A (en) * 2015-11-18 2016-01-13 苏州清然环保科技有限公司 Organic wastewater treatment device
CN106396077A (en) * 2016-11-07 2017-02-15 同济大学 Iron-based catalyst unitized packing for catalyzing ozonation

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