CN100591632C - A method and device for advanced treatment of printing and dyeing wastewater with ozone catalysis of iron and zinc - Google Patents
A method and device for advanced treatment of printing and dyeing wastewater with ozone catalysis of iron and zinc Download PDFInfo
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- 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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- 239000002351 wastewater Substances 0.000 title claims abstract description 130
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000011282 treatment Methods 0.000 title claims abstract description 62
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000004043 dyeing Methods 0.000 title claims abstract description 52
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 40
- 239000011701 zinc Substances 0.000 title claims abstract description 36
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 26
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 23
- 238000007639 printing Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 89
- 230000003197 catalytic effect Effects 0.000 claims abstract description 88
- 239000000945 filler Substances 0.000 claims abstract description 66
- 230000000694 effects Effects 0.000 claims abstract description 20
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 13
- 244000005700 microbiome Species 0.000 claims abstract description 11
- 238000011049 filling Methods 0.000 claims abstract description 10
- 238000005276 aerator Methods 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 239000005416 organic matter Substances 0.000 claims abstract 14
- 238000006065 biodegradation reaction Methods 0.000 claims abstract 4
- 238000012856 packing Methods 0.000 claims abstract 3
- 239000000463 material Substances 0.000 claims description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 26
- 229910052802 copper Inorganic materials 0.000 claims description 25
- 239000010949 copper Substances 0.000 claims description 25
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- -1 iron ions Chemical class 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 7
- 150000003384 small molecules Chemical class 0.000 claims description 7
- 238000005273 aeration Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000005189 flocculation Methods 0.000 claims description 5
- 230000016615 flocculation Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229910017827 Cu—Fe Inorganic materials 0.000 claims description 4
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 238000004065 wastewater treatment Methods 0.000 claims description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims 2
- 238000005192 partition Methods 0.000 claims 2
- 238000007747 plating Methods 0.000 claims 2
- 238000003672 processing method Methods 0.000 claims 1
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- 239000000047 product Substances 0.000 description 9
- 230000000630 rising effect Effects 0.000 description 7
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- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000001223 reverse osmosis Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 3
- 235000019398 chlorine dioxide Nutrition 0.000 description 3
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 3
- 208000028659 discharge Diseases 0.000 description 3
- 230000003311 flocculating effect Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
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- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 239000013043 chemical agent Substances 0.000 description 1
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- 229920005615 natural polymer Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
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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
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- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
本发明一种印染废水臭氧催化铁锌深度处理方法及装置，方法采用准备步骤、制作催化填料步骤、制作催化床步骤、废水充臭氧步骤、废水催化步骤、废水生物降解步骤、处理水输出步骤后，处理效果稳定，对印染废水中残留的杂环类有机物具有较强的分解能力；形成的合格水经出水管输出于处理池体外；装置包括处理池体，该处理池体的第一型腔的格栅体内填充有催化填料，第二型腔的格栅体内填充有微生物，并在第二型腔内形成曝气生物滤池，第一型腔位于格栅体的下方为进水腔，该进水腔同时连接有进水管和臭氧发生器的出气口；第一出水腔与进水腔之间配设有循环水泵；第二出水腔连接有出水管，还配设有曝气器；装置的运行过程可操作性强，自动化程度高。
The present invention is a method and device for advanced treatment of printing and dyeing wastewater with ozone catalysis of iron and zinc. The method adopts preparation steps, steps of making catalytic packing, step of making catalytic bed, step of filling wastewater with ozone, step of catalyzing wastewater, step of wastewater biodegradation, and step of outputting treated water. , the treatment effect is stable, and it has a strong ability to decompose the heterocyclic organic matter remaining in the printing and dyeing wastewater; the formed qualified water is output outside the treatment tank through the outlet pipe; the device includes a treatment tank body, the first cavity of the treatment tank body The grid body of the second cavity is filled with catalytic fillers, the grid body of the second cavity is filled with microorganisms, and a biological aerated filter is formed in the second cavity, and the first cavity is located below the grid body as the water inlet cavity. The water inlet chamber is connected with the water inlet pipe and the gas outlet of the ozone generator; a circulating water pump is arranged between the first water outlet chamber and the water inlet chamber; the second water outlet chamber is connected with a water outlet pipe and equipped with an aerator; The operation process of the device has strong operability and high degree of automation.
Description
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)
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|---|---|---|---|
| CN200810063462A CN100591632C (en) | 2008-08-07 | 2008-08-07 | A method and device for advanced treatment of printing and dyeing wastewater with ozone catalysis of iron and zinc |
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|---|---|---|---|
| CN200810063462A CN100591632C (en) | 2008-08-07 | 2008-08-07 | A method and device for advanced treatment of printing and dyeing wastewater with ozone catalysis of iron and zinc |
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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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