CN105198131A - Method for treating waste water through double catalytic oxidation process and device for achieving method - Google Patents
Method for treating waste water through double catalytic oxidation process and device for achieving method Download PDFInfo
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- CN105198131A CN105198131A CN201410249927.9A CN201410249927A CN105198131A CN 105198131 A CN105198131 A CN 105198131A CN 201410249927 A CN201410249927 A CN 201410249927A CN 105198131 A CN105198131 A CN 105198131A
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Abstract
The invention belongs to the field of waste water treatment, and particularly relates to a method for treating waste water through a double catalytic oxidation process. A catalyst is added to the waste water for sodium hypochlorite catalytic oxidation, and then electrolytic catalysis is carried out. Gamma-Al2O3 is adopted as a carrier of the catalyst, and oxide loaded with one or more of Mn element, Cu element, Fe element, Co element, Ce element and K element is adopted as an active component of the catalyst. When the catalyst is added to the waste water for sodium hypochlorite catalytic oxidation, sodium hypochlorite is preferably added. Organic matter with weak oxidation resistance in the waste water is firstly subjected to catalytic oxidation decomposition through sodium hypochlorite, and organic matter with high oxidation resistance is subjected to electrolytic catalytic oxidation degradation later on. The organic matter in the waste water is treated in a classification mode through the double catalytic oxidation process, the hydraulic retention time is shortened, and treatment efficiency is improved. The invention further provides a device for achieving the method. The device is simple in structure and easy to implement.
Description
Technical field
The invention belongs to field of waste water treatment, be specifically related to a kind of double catalytic oxidation art breading method for waste water and device thereof.
Background technology
Along with developing rapidly of modern industry, the trade effluent produced the not only water yield increases, and towards trend developments such as complicated component, inorganic salt content height.At present, mostly adopt the biological process of better economy to process to the treatment process of trade effluent both at home and abroad, but along with the increasingly stringent of various places emission standard, depend merely on the especially high salinity of biochemical process process, used water difficult to degradate is difficult to reach discharge index requirement.
Process for high salinity, used water difficult to degradate is a focus of Chinese scholars research recent years.For reaching higher treating depth, normal physical adsorption and the chemical oxidation process of adopting processes this type of waste water.Physical adsorption mainly comprises charcoal absorption and resin absorption, but the shortcoming that these class methods exist needs its regeneration after to be sorbing material absorption saturated, and regenerative process not only energy consumption is high, and regenerated liquid is generally containing high-enriched organics, causes secondary pollution; Conventional chemical oxidation mainly advanced oxidation processes, but this technique is short owing to exploring the time, basic theory is also very imperfect, and it is various to add actual contaminated system complexity, makes this technology all there is the problem much requiring study and solve in theoretical investigation or industrial application.
The advantage that high-level oxidation technology has biological process and Physical etc. incomparable in process waste water, has the advantages such as efficiency is high, degree for the treatment of is dark.But the shortcomings such as facility investment is large, complicated operation, working cost are high that most of high-level oxidation technology exists, as wet-type oxidation technology needs to run under high-temperature and high-pressure conditions, facility investment and energy consumption higher; In ozonation technology ozonizer stability requirement high and run in power consumption large; Fenton reagent oxidizing process complicated operation and consume a large amount of chemical agent.
Catalytic oxidation technique refers to and adopts catalyzer to improve oxidation efficiency in advanced oxidation processes, reduces the activation energy of reaction, makes oxidizing reaction can obtain gratifying effect at normal temperatures and pressures.But because the organism kinds in waste water is more, the phenomenon such as the high or treating depth of processing costs is poor that only adopts a certain catalytic oxidation technique still to exist.So according to the feature of waste component complexity, the method adopting several catalytic oxidation technique to combine processes it, can obtain desirable treatment effect, effectively can reduce processing costs again.
Hypochlorite oxidation is that the hypochlorous acid utilizing clorox to be hydrolyzed formation carries out oxidative degradation to Organic substance in water by clorox adding of agent in waste water.Clorox catalyzed oxidation is in hypochlorite oxidation technique, introduce the shortcomings such as catalyst filling forms fixed bed, and the degree for the treatment of avoiding traditional hypochlorite oxidation is low, dosing is large; Electrolytic oxidation is under the effect of applying direct current electric field, utilizes electrode surface and organism to carry out electronic migration and directly to degrade to organism or the oxidizing substance that utilizes electrode to produce such as hydroxyl radical free radical (OH), state oxygen of living (O), hypochlorous acid etc. are degraded indirectly to organism.Catalytic and oxidative electrolysis technology refer to adopt that the ti-based coating electrode with catalysis is positive pole, stainless steel or other electrode be the oxidizing process of negative pole.Because ti-based coating electrode has higher oxidizing potential, so catalytic and oxidative electrolysis technology has higher oxidation capacity than clorox catalyzed oxidation.
Organism complexity in waste water is various, its resistance of oxidation is strong and weak different, independent employing clorox catalytic oxidation technique processes, under the prerequisite adding clorox medicament, the weak organism of Partial Antioxidation ability is degraded, and the strong organism of resistance of oxidation is difficult to be degraded, treating depth is inadequate; Independent employing catalytic and oxidative electrolysis technology, first the weak organism of resistance of oxidation is degraded, then the organism that resistance of oxidation is strong is degraded again, a large amount of electric energy is consumed in electrolytic process, processing costs is high, if processed after this two kinds of catalytic oxidation techniques combination waste water, the weak organism of resistance of oxidation is first by clorox catalyzing oxidizing degrading, and the organism that resistance of oxidation is strong is degraded by catalytic and oxidative electrolysis technology subsequently.And the clorox medicament added in clorox catalytic oxidation technique and organism react after become chlorion be dissolved in water improve catalytic and oxidative electrolysis technology technique intake in specific conductivity, the bath voltage of catalytic and oxidative electrolysis technology can be reduced, reduce power consumption; And the chlorion electrolysis in waste water can be hypochlorous acid by catalytic and oxidative electrolysis technology process section, be partly refluxed to the alternative or Some substitute clorox of clorox catalytic oxidation technique section again containing hypochlorous electrolysis water outlet, reduce dosing.So be core with clorox catalyzed oxidation and catalytic and oxidative electrolysis technology, double catalytic oxidation technique not only carries out " classification " degraded according to the difference of oxidation operation difficulty to it, and define chlorine element " useful internal recycle " in process, the treating depth to waste water can be reached, effectively can reduce processing cost again.
Patent CN103539225A discloses a kind of the Internal Circulating Fluidized Bed electric catalysis reactor and the operational conditions that process chemical industrial organic wastewater, and this reactor is by electrolyzer, electrode slot, the supporting Pt titanium substrate anode plate, stainless steel cathode plate, the loaded Ag doped with Mn O containing CuO middle layer that modify based on NiO-FeO-ZnO
2-CeO
2activated alumina granule electrode, surge hopper, inlet pipe, electric wire and current regulator power supply form.The top of surge hopper is connected with the bottom of electrolyzer, is installed into tracheae in the bottom of surge hopper.Electrolyzer is provided with 4 electrode slots altogether, for the supporting Pt titanium substrate anode plate inserting stainless steel cathode plate and modify based on NiO-FeO-ZnO, by the loaded Ag doped with Mn O containing CuO middle layer
2-CeO
2activated alumina granule electrode evenly drops in electrolyzer.In this patent, activated alumina granule electrode is dropped in electrolyzer, the voltage between pole plate can be increased, increase electrolytic power consumption, and second stage employ is not carried out to the clorox that process produces containing high-chlorine organic wastewater electrolysis, treating depth and processing costs higher.
Patent CN102921424A discloses a kind of catalyzer, LX catalysed oxidation processes and antibiotic waste water treatment process, this catalyzer is formed by proportioning sintering by nickel, cobalt and tripoli, use above-mentioned catalyzer, in organic waste water, add hypochlorous acid or hypochlorite and above-mentioned catalyzer, produce catalyzed reaction.Adopt multi-dimensional electro-catalytic oxidation style to carry out pre-treatment to high-concentration waste water, adopt anaerobic digestion to carry out pre-treatment to bacterium slag filtrate; The high-concentration waste water adopting the process of LX efficiently catalyzing and oxidizing method process previous step to obtain and the mixed solution of bacterium slag filtrate; Conveniently the comprehensive wastewater that obtain of technique to previous step processes.Method of wastewater treatment technical process disclosed in this patent is complicated, to the bad adaptability of waste water, is only suitable for processing described waste water and similar waste water; Hypochlorous acid when not producing wastewater electrolytic carries out second stage employ, and processing costs is high.
Document " Pestcide Wastewater Containing Chlorosulfuron Treated By Electrolyte And Catalytic Oxidation Process " [Fu Xueqi etc., water technology, 1997 (2)] with the grand agricultural chemicals waste water of green sulphur after desulfurization process for research object, by its electrolysis, the NaClO produced with electrolysis is for oxygenant, and the oxide compound of nickel is catalyzer, carry out catalytic oxidation treatment, reduce the COD value of waste water greatly, and make waste water have good biochemical treatment, then with Wastewater Treated by Activated Sludge Process, make it to reach emission standard.Treatment process described in the document is to hypochlorous acid oxidization after the first electrolysis of waste water, although make use of the hypochlorous acid of electrolysis generation, be not oxidized according to the order of useless Organic substance in water " easy first and difficult later ", treating depth is low, and processing costs is simultaneously high; For chloride ion content, waste water that is low or not chloride ion-containing adopts this technique then poor processing effect, so the bad adaptability to waste water.
Summary of the invention
For the deficiencies in the prior art, the object of this invention is to provide a kind of double catalytic oxidation art breading method for waste water, the treating depth to waste water can be reached, effectively can reduce processing cost again; The present invention also provides a kind of device realizing the method, and structure is simple, easy to implement.
Double catalytic oxidation art breading method for waste water of the present invention, adds catalyzer and carries out clorox catalyzed oxidation, then carry out electrolytic catalysis in waste water.
If chlorine ion concentration is lower in pending waste water, adds in waste water when catalyzer carries out clorox catalyzed oxidation and also add clorox.If the chlorion containing higher concentration in pending waste water, do not need to add clorox.When in general pending waste water, chlorine ion concentration is greater than 5000mg/L, do not need to add clorox.The volume ratio of catalyzer and waste water is 50% ~ 200%, and clorox weight is 0 ~ 0.2% of waste water, is preferably 0.1%.
Catalyzer is with γ-Al
2o
3for carrier, the oxide compound of one or more in load Mn, Cu, Fe, Co, Ce, K or Ce element is as active constituent.
Electrolytic catalysis anode material is ti-based coating electrode, and coating consists of PbO
2, IrO
2, RuO
2, SnO
2or TaO
2one or more, cathode material is the one in stainless steel, graphite, titanium net or titanium plate.
In electrolytic catalysis, the spacing of positive electrode and negative potential is 2-4cm, plate current density 2-5mA/cm
2.
A kind of device realizing described double catalytic oxidation art breading method for waste water, comprise clorox catalyst oxidation reactor and catalytic and oxidative electrolysis technology reactor, water inlet pipe is connected bottom clorox catalyst oxidation reactor, water inlet pipe is provided with intake pump, clorox storage tank connects dosing volume pump and water inlet pipe successively by pipeline, clorox catalyst oxidation reactor top connects catalytic and oxidative electrolysis technology reactor top by upflow tube, catalytic and oxidative electrolysis technology reactor connects rising pipe, catalytic and oxidative electrolysis technology inside reactor arranges anode and negative electrode, anode is all connected with direct supply with negative electrode.
Wherein: be communicated with by return line between rising pipe with water inlet pipe, return line is provided with backflow volume pump.
The clorox that pending waste water first adds in clorox storage tank enters clorox catalyst oxidation reactor through water inlet pipe, the weak organism of resistance of oxidation is first by clorox catalyzing oxidizing degrading, water outlet enters catalytic and oxidative electrolysis technology reactor, the organism that resistance of oxidation is strong is degraded by catalytic and oxidative electrolysis technology, and catalytic and oxidative electrolysis technology water part is discharged, is partly refluxed to clorox catalyst oxidation reactor water-in.Be converted into chlorion after organism in the clorox added in clorox catalyzed oxidation section and waste water reacts, improve follow-up catalytic and oxidative electrolysis technology technique and enter electrical conductivity of water, the bath voltage of catalytic and oxidative electrolysis technology can be reduced, reduce power consumption; Chlorion in waste water is converted into hypochlorite again by catalytic and oxidative electrolysis technology section again, and the electrolysis water outlet of this section is partly refluxed to the alternative or Some substitute clorox of clorox catalyzed oxidation section again, reduces clorox dosing.If the chlorion containing higher concentration in pending waste water, then the dosage or the stopping that reducing clorox add clorox, strengthen the quantity of reflux between catalytic and oxidative electrolysis technology water outlet to hypochlorous acid catalyzed oxidation water inlet simultaneously; If in pending waste water not chloride ion-containing or content low, then strengthen the dosage of clorox, reduce simultaneously or close the quantity of reflux between catalytic and oxidative electrolysis technology water outlet to clorox catalyzed oxidation water inlet, while guarantee treatment effect, reducing processing cost to greatest extent.
The present invention utilizes clorox catalyzed oxidation and catalytic and oxidative electrolysis technology combination process to process waste water for core.In treating processes, according to the difference of oxidation operation difficulty, " classification " degraded is carried out to it, and define chlorine element " useful internal recycle " in process, the treating depth to waste water can be reached, effectively can reduce processing cost again.
The present invention utilizes clorox catalyzed oxidation and catalytic and oxidative electrolysis technology combination process to process waste water for core.Pending waste water first adds clorox and enters clorox catalyst oxidation reactor, the weak organism of resistance of oxidation is first by clorox catalyzing oxidizing degrading, water outlet enters catalytic and oxidative electrolysis technology reactor, the organism that resistance of oxidation is strong is degraded by catalytic and oxidative electrolysis technology, and catalytic and oxidative electrolysis technology water part is discharged, is partly refluxed to clorox catalyst oxidation reactor water-in.
In sum, the present invention has the following advantages:
(1) the organism complexity in waste water is various, and its resistance of oxidation is strong and weak different, and the weak organism of resistance of oxidation is first by clorox catalyzing oxidizing degrading, and the organism that resistance of oxidation is strong is degraded by catalytic and oxidative electrolysis technology subsequently.Double catalytic oxidation technique, to useless Organic substance in water " classification " process, shortens hydraulic detention time, improves processing efficiency.
(2) can according to the water quality characteristics flexible operating of pending waste water, if the chlorion containing higher concentration in pending waste water, the dosage or the stopping that then reducing clorox add clorox, strengthen the quantity of reflux between catalytic and oxidative electrolysis technology water outlet to clorox catalyzed oxidation water inlet simultaneously; If in pending waste water not chloride ion-containing or content low, then strengthen the dosage of clorox, reduce the quantity of reflux between catalytic and oxidative electrolysis technology water outlet to clorox catalyzed oxidation water inlet simultaneously.
(3) become after the clorox medicament added in clorox catalytic oxidation technique and organism react chlorion be dissolved in water improve catalytic and oxidative electrolysis technology technique intake in specific conductivity, the bath voltage of catalytic and oxidative electrolysis technology can be reduced, reduce power consumption; And the chlorion electrolysis can fallen in waste water of catalytic and oxidative electrolysis technology process section is hypochlorous acid, alternative or the Some substitute clorox of clorox catalytic oxidation technique section is partly refluxed to again containing hypochlorous electrolysis water outlet, reduce dosing, define chlorine element " useful internal recycle " in process, effectively reduce processing costs.
(4) the present invention also provides a kind of device realizing the method, and structure is simple, easy to implement.
Accompanying drawing explanation
Fig. 1 is the device of described double catalytic oxidation art breading method for waste water.
In figure: 1-water inlet pipe; 2-intake pump; 3-dosing volume pump; 4-clorox storage tank; 5-clorox catalyst oxidation reactor; 6-clorox special-purpose catalyst; 7-upflow tube; 8-direct supply; 9-catalytic and oxidative electrolysis technology reactor; 10-anode; 11-negative electrode; 12-refluxes volume pump; 13-return line; 14-rising pipe.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
The biochemical waste water in certain rubber plant's sewage butylbenzene workshop: water yield 150m
3/ h, COD are 95mg/L, and specific conductivity is 5500 μ s/cm, and chloride ion content is 110mg/L.
The device of double catalytic oxidation art breading method for waste water: as shown in Figure 1, comprise clorox catalyst oxidation reactor 5 and catalytic and oxidative electrolysis technology reactor 9, water inlet pipe 1 is connected bottom clorox catalyst oxidation reactor 5, water inlet pipe 1 is provided with intake pump 2, clorox storage tank 4 connects dosing volume pump 3 and water inlet pipe 1 successively by pipeline, clorox catalyst oxidation reactor 5 top connects catalytic and oxidative electrolysis technology reactor 9 top by upflow tube 7, catalytic and oxidative electrolysis technology reactor 9 connects rising pipe 14, be communicated with by return line 13 between rising pipe 14 with water inlet pipe 1, return line 13 is provided with backflow volume pump 12, catalytic and oxidative electrolysis technology reactor 9 inside arranges anode 10 and negative electrode 11, anode 10 is all connected with direct supply 8 with negative electrode 11.
Used catalyst is with γ-Al
2o
3for carrier, load Manganse Dioxide is active constituent.The volume ratio of catalyzer and waste water is 50%, and clorox weight is 0.2% of waste water.Electrolytic catalysis anode material is ti-based coating electrode, and coating consists of PbO
2, cathode material is stainless steel.
Treating processes: pending waste water enters 150m by water inlet pipe 1 through intake pump 2
3bottom clorox catalyst oxidation reactor 5, bottom-up flow through catalyzer 6 packing layer after enter into 75m by upflow tube 7
3catalytic and oxidative electrolysis technology reactor 9, direct supply 8 positive pole ligation device Anodic 10, negative pole connects negative electrode 11, and the spacing between anode 10 and negative electrode 11 is 4cm, plate current density 2mA/cm
2, catalytic and oxidative electrolysis technology water outlet is flowed out from rising pipe 14.While entering waste water, clorox enters water inlet pipe 1 through dosing volume pump 3 according to 100mg/L from clorox storage tank 4, and closing volume volume pump 12 stops internal reflux.Water outlet water yield 150m
3/ h, COD are 24mg/L, and specific conductivity is 5420 μ s/cm, and chloride ion content is 186mg/L, and processing costs is 1.8 yuan/m
3.
Embodiment 2
The reverse osmosis concentrated water in certain Reuse of Waste Water In Refineries workshop: water yield 100m
3/ h, COD are 120mg/L, and specific conductivity is 8500 μ s/cm, and chloride ion content is 1200mg/L.
The device of the double catalytic oxidation art breading method for waste water that embodiment 2 is used is identical with embodiment 1.
Used catalyst is with γ-Al
2o
3for carrier, loaded copper oxide is active constituent.Catalyzer is 200% in the volume ratio of waste water, and clorox weight is 0.1% of waste water.Electrolytic catalysis anode material is ti-based coating electrode, and coating consists of IrO
2, cathode material is titanium net.
Treating processes: pending waste water enters 100m by water inlet pipe 1 through intake pump 2
3bottom clorox catalyst oxidation reactor 5, bottom-up flow through clorox special-purpose catalyst 6 packing layer after enter into 50m by upflow tube 7
3catalytic and oxidative electrolysis technology reactor 9, direct supply 8 positive pole ligation device Anodic 10, negative pole connects negative electrode 11, and the spacing between anode 10 and negative electrode 11 is 3cm, plate current density 3mA/cm
2, catalytic and oxidative electrolysis technology water outlet is flowed out from rising pipe 14.Water inlet while, clorox enters water inlet pipe 1 through dosing volume pump 3 according to 50mg/L from clorox storage tank 4, catalytic and oxidative electrolysis technology water outlet through backflow volume pump 12 according to 20m
3/ h enters water inlet pipe 1 by return line 13.Water outlet water yield 100m
3/ h, COD are 30mg/L, and specific conductivity is 8420 μ s/cm, and chloride ion content is 1310mg/L, and processing costs is 2.0 yuan/m
3.
Embodiment 3
Certain rare-earth smelting factory extraction plant waste water: water yield 200m
3/ h, COD are 220mg/L, and specific conductivity is 41000 μ s/cm, and chloride ion content is 16000mg/L.
The device of the double catalytic oxidation art breading method for waste water that embodiment 3 is used is identical with embodiment 1.
Used catalyst is with γ-Al
2o
3for carrier, load ferric oxide and cobalt oxide are active constituent.Catalyzer is 100% in the volume ratio of waste water, and clorox weight is 0.01% of waste water.Electrolytic catalysis anode material is ti-based coating electrode, and coating consists of SnO
2, cathode material is titanium plate.
Treating processes: pending waste water enters 400m by water inlet pipe 1 through intake pump 2
3bottom hypochlorous acid catalyst oxidation reactor 5, bottom-up flow through hypochlorous acid special-purpose catalyst 6 packing layer after enter into 200m by upflow tube 7
3catalytic and oxidative electrolysis technology reactor 9, direct supply 8 positive pole ligation device Anodic 10, negative pole connects negative electrode 11, and the spacing between anode 10 and negative electrode 11 is 2cm, plate current density 5mA/cm
2, catalytic and oxidative electrolysis technology water outlet is flowed out from rising pipe 14.While water inlet, close dosing volume pump 3, stop adding clorox; Catalytic and oxidative electrolysis technology water outlet through backflow volume pump 12 according to 100m
3/ h enters water inlet pipe 1 by return line 13.Water outlet water yield 200m
3/ h, COD are 32mg/L, and specific conductivity is 3990 μ s/cm, and chloride ion content is 15200mg/L, and processing costs is 3.0 yuan/m
3.
Claims (7)
1. a double catalytic oxidation art breading method for waste water, is characterized in that: in waste water, add catalyzer carry out clorox catalyzed oxidation, then carry out electrolytic catalysis.
2. double catalytic oxidation art breading method for waste water according to claim 1, is characterized in that: catalyzer is with γ-Al
2o
3for carrier, the oxide compound of one or more in load Mn, Cu, Fe, Co, Ce, K or Ce element is as active constituent.
3. double catalytic oxidation art breading method for waste water according to claim 2, is characterized in that: add in waste water when catalyzer carries out clorox catalyzed oxidation and also add clorox.
4. the method for double catalytic oxidation art breading waste water according to claim 1, is characterized in that: electrolytic catalysis anode material is ti-based coating electrode, and coating consists of PbO
2, IrO
2, RuO
2, SnO
2or TaO
2one or more, cathode material is the one in stainless steel, graphite, titanium net or titanium plate.
5. the method for double catalytic oxidation art breading waste water according to claim 1, is characterized in that: in electrolytic catalysis, the spacing of positive electrode and negative potential is 2-4cm, plate current density 2-5mA/cm
2.
6. realize a device for the arbitrary described double catalytic oxidation art breading method for waste water of claim 1-5, it is characterized in that:
Comprise clorox catalyst oxidation reactor (5) and catalytic and oxidative electrolysis technology reactor (9), clorox catalyst oxidation reactor (5) bottom connects water inlet pipe (1), water inlet pipe (1) is provided with intake pump (2), clorox storage tank (4) connects dosing volume pump (3) and water inlet pipe (1) successively by pipeline, clorox catalyst oxidation reactor (5) top connects catalytic and oxidative electrolysis technology reactor (9) top by upflow tube (7), catalytic and oxidative electrolysis technology reactor (9) connects rising pipe (14), catalytic and oxidative electrolysis technology reactor (9) inside arranges anode (10) and negative electrode (11), anode (10) is all connected with direct supply (8) with negative electrode (11).
7. the device of double catalytic oxidation art breading method for waste water according to claim 6, it is characterized in that: be communicated with by return line (13) between rising pipe (14) with water inlet pipe (1), return line (13) is provided with backflow volume pump (12).
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