CN103121737B - Method for electrochemically treating printing and dyeing wastewater - Google Patents
Method for electrochemically treating printing and dyeing wastewater Download PDFInfo
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- CN103121737B CN103121737B CN201310054569.1A CN201310054569A CN103121737B CN 103121737 B CN103121737 B CN 103121737B CN 201310054569 A CN201310054569 A CN 201310054569A CN 103121737 B CN103121737 B CN 103121737B
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- titanium
- rare earth
- waste water
- oxide electrode
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Abstract
The invention discloses a method for electrochemically treating printing and dyeing wastewater. The method comprises the following steps of: preparing a titanium-based oxide electrode; polishing the titanium-based body by abrasive paper to remove the greasy dirt from the surface of the titanium-based body; washing the titanium-based body with water and etching the titanium-based body by using a sulfuric acid solution; preparing a precursor containing rear-earth cobaltates; dissolving ruthenium chloride in the alcohol at room temperature, adding butyl titanate for sufficiently stirring the mixed solution, and adding solid rear-earth cobaltates for sufficiently stirring the mixed solution to obtain the precursor containing the rear-earth ruthenium cobalt; preparing a titanium-based oxide electrode, wherein the prepared precursor containing the rear-earth ruthenium cobalt is coated on the pretreated titanium base body, kept in an oven, transferred to a muffle furnace for being roasted and continuously coated after being naturally cooled; the process is repeated many times, and the oxide electrode of the titanium-based rear-earth ruthenium cobalt is obtained by roasting at the last time; with the prepared oxide electrode of the titanium-based rear-earth ruthenium cobalt as an anode and a stainless steel strip serving as a cathode, carrying out titanium anode oxidation treatment on the industrial printing and dyeing pigment in the wastewater, wherein the discoloring effect of the pigment is higher than 96%.
Description
Technical field
The present invention relates to a kind of method of processing dyeing wastewater, object is to process difficult problem for high-concentration and high-chromaticity refractory dyeing waste water, belongs to field of environment protection, adopts catalytic oxidation, i.e. titanium anonizing.The feature of this titanium anode is the rare earth oxide that surface deposition is coated with perovskite structure, and this anode can further improve electrode performance; The method adopts circulation device, and the contact surface that increases electrode reduces concentration potential and improves electric utilization ratio.
Background technology
1. about the processing of organic waste water
Along with the development of dyeing, produced a large amount of organism dyeing waste waters.Although traditional bioremediation is used widely aspect organic matter removal, biologic treating technique can only be removed the biological organism mixing in water body effectively in essence, inapplicable to the increasing abiotic material that mixes.At present printing and dyeing enterprise is mainly processed with coagulant sedimentation, and the method produces a large amount of sediments, and the method belongs to nondestructive method, and oxious component is not removed from environment.Can say that the Industrial Wastewater Treatment such as printing and dyeing still lack economy and effective means so far.The application of electrolytic catalysis treatment technology in treatment of dyeing wastewater, has real meaning in solution Dying Wastewater Treatment & problem.
At present, domestic treatment of dyeing wastewater means be take biochemical process as main, and what have also connects chemical method, Physical with it.
Physical treatment process is mainly to take absorption method as main, this method is that the powder of the porous masses such as gac, clay or particle are mixed with waste water, or allow waste water pass through the filter bed that its granular substance forms, make pollution substance in waste water be attracted on porous mass surface or be filtered and remove.Its shortcoming is that body refuse generation is large, and further intractability is large.
Method of chemical treatment Coagulation Method Coagulation Method mainly contains coagulant sedimentation and mixed condensed gas flotation process, the coagulating agent adopting be take aluminium salt or molysite mostly as main, shortcoming is that working cost is higher, body refuse amount many and dehydration is difficult, hydrophilic dye poor processing effect, and oxidation style mainly contains the several methods such as ozone oxidation and photooxidation method.From domestic and international service experience and result, this method good decolorizing effect, but power consumption is many, and large-scale promotion application has certain difficulty.
Traditional biological treatment has aerobic and Anaerobic biotreatment method, but can not meet the demand of dyeing, dyeing waste water, as the organic waste water of high density, generally all should not directly carry out biological method processing, thereby occur as pretreated chemical treatment method.Common chemical treatment method in waste water, drop into exactly chemical agent (as, materials such as molysite) make it with waste water in substance reaction, generate precipitation or neutralizing acid basicity.But as chemical treatment, need to add a large amount of medicaments in waste water, the medicament especially for precipitation, easily produces some poisonous precipitations, causes secondary pollution, and precipitation process can produce a large amount of solids again simultaneously.
Adopt catalytic oxidation, be that electrochemical process is disposed of sewage and can be operated at normal temperatures and pressures, generally there is, investment simple, easy to operate without a lot of pharmaceutical chemicalss, equipment and working cost is cheap, floor space is little, sludge quantity seldom and the advantage such as environmental compatible, thereby caused investigator's extensive attention.In recent years, domestic and foreign literature has all reported that electrochemical method administers various waste water and succeed.
2. about the research of electrode materials
In the test of disposing of sewage in electrolytic process, the selection of electrode has a variety of, wherein selects the in the majority of the traditional electrode such as graphite, platinum, plumbic oxide.But expansion to some extent in recent years, reference is reported discovery selection for electrode in catalytic oxidation process with the technology of following the tracks of domestic and international advanced person, mainly concentrate on and take on the novel active negative electrode that the novel active anode that titanium is substrate (belonging to Dimensional Stable Anodes, DSA class electrode) and the iron of take is substrate.As titanium combined electrode, when the percent of decolourization of waste water from dyestuff is 90%, its power consumption is only 1.1 kwhm
-3.
Summary of the invention
The object of this invention is to provide a kind of By Electrocatalytic Oxidation and process the method for dyeing wastewater, adopt titanium anonizing.The feature of this titanium anode is the rare earth oxide that surface deposition is coated with perovskite structure, and this anode can further improve electrode performance; The method adopts circulation device, and the contact surface that increases electrode reduces concentration potential and improves electric utilization ratio.
The object of the present invention is achieved like this, described
a method for electrochemical treatment dyeing waste water, comprises the steps:
(1) prepare titanium-based oxide electrode
Titanium matrix (titanium plate, titanium rod, titanium net etc.) carries out pre-treatment, and titanium matrix is first used to sand papering, removes surperficial oxide compound; Use NaOH-NaCO
3mixed solution boils 10-60 minute by titanium material, depending on the amount of greasy dirt, suitably increases boiling time, removes surperficial greasy dirt; After taking out, with a large amount of water, rinse, then with sulphuric acid soln, titanium plate is carried out to etching, increase titanium plate specific surface area.Above-mentioned sulphuric acid soln concentration can be the normally used concentration in this area, and it is that 1:1 is formulated by volume that the present invention preferably adopts the vitriol oil that water and weight percent concentration are 98%.Described NaOH-NaCO
3mixed solution can adopt the normally used concentration in this area, the preferred NaOH-NaCO of the present invention
3in mixed solution, the weight ratio of sodium hydroxide and sodium carbonate is 1:1.
Preparation contains the presoma of rare earth cobaltic trioxide: at room temperature, a certain amount of ruthenium chloride is dissolved in to ethanol, then add butyl (tetra) titanate,, fully stir, add again afterwards solid rare earth cobaltates (particle diameter 18-50nm), the mol ratio of rare earth cobaltic trioxide, ruthenium chloride, butyl (tetra) titanate, ethanol is (1-3:2.5-3:4-6:1000), stir 1-2 hour, standing 12 hours to 3 days, make the presoma containing rare earth ruthenium cobalt.Rare earth cobaltic trioxide can adopt the normally used rare earth cobaltic trioxide in this area, the preferred cobalt acid of the present invention lanthanum.Described ethanol can be the normally used concentration in this area, and the present invention preferably adopts dehydrated alcohol.
Prepare titanium-based oxide electrode: the presoma containing rare earth ruthenium cobalt is coated on pretreated titanium matrix, first in 100-150 ℃ of baking oven, keep 5-10 minute, then proceed to roasting 5-10 minute in the retort furnace of 450-550 ℃, take out, in air, cooling rear continuation applies, 5-25 time repeatedly, last in the retort furnace of 450-550 ℃ roasting 30-60 minute, make the oxide electrode of titanium base rare earth ruthenium cobalt.
(2) wastewater treatment
The oxide electrode of titanium base rare earth ruthenium cobalt prepared by employing step (1) is anode, and stainless steel strip is negative electrode, in waste water, industry printing and dyeing pigment is carried out to titanium anodic oxidation treatment.By changing current density and the residence time, make the COD of electrolytic reaction water outlet
crconcentration is less than 60mg/L, and colourity is less than 30 o'clock qualified discharges, recycles, thereby realizes the object that dyeing waste water electricity decomposes advanced treatment and reclamation.Described step (2)
'sin wastewater treatment, industry printing and dyeing pigment concentration is 100-500mgL
-1, the current density of controlling in titanium anodic oxidation treatment is 50-300Am
-2, electrolysis time is 20-120 minute, percent of decolourization reaches more than 95%.
Advantage of the present invention is:
Main several main points: adopt electrolysis, treatment scheme is simplified, simple in structure, does not need to add too many medicament, has reduced cost
Adopt rare earth Ti/LaCoO
3+ Ru
2o
3+ TiO
2electrode, the reaction times is short, and energy consumption is low;
Can make the decolouring of most of reactive dyestuffs, degraded, removal efficiency is high, and this can process the dyeing waste water of high-concentration and high-chromaticity, has expanded range of application.
Embodiment
(1) prepare titanium-based oxide electrode
Get strip titanium plate, with after sand papering; Put into 500ml and contain 10gNaOH and 10g Na
2cO
3in mixed solution, boil 30 minutes, take out and use respectively tap water and distilled water flushing; Then the vitriol oil that water and weight percent concentration are 98% is by volume for the sulphuric acid soln that 1:1 is mixed with carries out etching to titanium plate.
Preparation contains the presoma of rare earth cobaltic trioxide:
Titanium base rare earth ruthenium cobalt/cobalt oxide coating adopts containing the presoma of rare earth cobaltic trioxide to be prepared by the method for thermolysis.The preparation of presoma: at room temperature ruthenium chloride and butyl (tetra) titanate are dissolved in respectively to dehydrated alcohol, fully mix after stirring respectively, add again lanthanum cobalt powder (particle diameter 18-50nm) under stirring state.The mol ratio of cobalt acid lanthanum, ruthenium chloride, butyl (tetra) titanate, dehydrated alcohol is 2:3:5:1000, after above-mentioned 4 kinds of materials mix, continues to stir 2 hours, standing 2 days, makes the presoma containing rare earth ruthenium cobalt.The presoma containing rare earth ruthenium cobalt making is coated on pretreated titanium matrix, first in 100 ℃ of baking ovens, keep 5 minutes, then proceed in the retort furnace of 500 ℃ roasting 5 minutes, take out, cooling in air, rear continuation applies, 10 times repeatedly, last roasting 120 minutes in the retort furnace of 500 ℃, makes titanium base rare earth ruthenium cobalt/cobalt oxide electrode.
(2) wastewater treatment
In waste water, pigment concentration is 100mgL
-1, the oxide electrode of titanium base rare earth ruthenium cobalt prepared by employing step (1) is anode, and stainless steel strip is negative electrode, and at room temperature, control current density is 150Am
-2, electrolysis 20-120 minute.
The electrode adopting in the present invention---titanium base rare earth ruthenium cobalt/cobalt oxide electrode (Ti/LaCoO
3+ Ru
2o
3+ TiO
2) decolorizing effect of several dyestuffs be the results are shown in to table 1.As can be seen from Table 1, take electrode of the present invention as anode, electrolytic oxidation is processed dye decolored effect and is all reached more than 96%.
Several active dye wastewater electrolysis process of table 1 rate (%) (reactive dyestuffs from Shanghai she Man)
Claims (6)
1. a method for electrochemical treatment dyeing waste water, comprises the steps:
1) prepare titanium-based oxide electrode:
Titanium matrix carries out pre-treatment, and titanium matrix is first used to sand papering, removes surperficial oxide compound; With NaOH and Na
2cO
3the mixed solution being mixed with boils 10-60 minute by titanium matrix, removes surperficial greasy dirt; After taking out, with a large amount of water, rinse, then with sulphuric acid soln, titanium matrix is carried out to etching, increase titanium matrix specific surface area;
Preparation contains the presoma of rare earth cobaltic trioxide: at room temperature, a certain amount of ruthenium chloride is dissolved in to ethanol, then add butyl (tetra) titanate, fully stir, adding afterwards particle diameter is the solid rare earth cobaltates of 18-50nm again, the mol ratio of described solid rare earth cobaltates, ruthenium chloride, butyl (tetra) titanate, ethanol is (1-3: 2.5-3: 4-6: 1000), fully stir 1-2 hour, make the presoma containing rare earth ruthenium cobalt; Described rare earth cobaltic trioxide adopts cobalt acid lanthanum;
Prepare titanium-based oxide electrode: the above-mentioned presoma containing rare earth ruthenium cobalt making is coated on pretreated titanium matrix, first in 100-150 ℃ of baking oven, keep 5-20 minute, then proceed to roasting 5-20 minute in the retort furnace of 450-600 ℃, after naturally cooling, continue to apply, 5-20 time repeatedly, last roasting 30-60 minute, makes the oxide electrode of titanium base rare earth ruthenium cobalt;
2) wastewater treatment:
The oxide electrode of the titanium base rare earth ruthenium cobalt of employing step 1) preparing is anode, and stainless steel strip is negative electrode, in waste water, industrial printing dye is carried out to titanium anodic oxidation treatment; In described wastewater treatment, industrial printing dye concentration is 100-500mgL
-1, the current density of controlling in titanium anodic oxidation treatment is 50-300Am
-2, electrolysis time is 20-120 minute, percent of decolourization reaches more than 95%.
2. the method for a kind of electrochemical treatment dyeing waste water according to claim 1, is characterized in that: the COD that works as electrolytic reaction water outlet in wastewater treatment described step 2)
crconcentration is less than 60mg/L, and colourity is less than at 30 o'clock, gets final product qualified discharge.
3. the method for a kind of electrochemical treatment dyeing waste water according to claim 1 and 2, is characterized in that: titanium matrix adopting titanium plate, titanium rod or titanium net.
4. the method for a kind of electrochemical treatment dyeing waste water according to claim 1 and 2, is characterized in that: it is what be mixed with at 1: 1 by volume that sulphuric acid soln described step 1) adopts the vitriol oil that water and weight percent concentration are 98%.
5. the method for a kind of electrochemical treatment dyeing waste water according to claim 1 and 2, is characterized in that: NaOH-Na described step 1)
2cO
3in mixed solution, sodium hydroxide and sodium carbonate are mixed with by weight at 1: 1.
6. the method for a kind of electrochemical treatment dyeing waste water according to claim 5, is characterized in that: at 500ml NaOH-Na
2cO
3in mixed solution, contain 10g sodium hydroxide and 10g sodium carbonate.
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| CN201310054569.1A CN103121737B (en) | 2013-02-21 | 2013-02-21 | Method for electrochemically treating printing and dyeing wastewater |
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| CN103121737B true CN103121737B (en) | 2014-05-07 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105084467A (en) * | 2014-05-05 | 2015-11-25 | 潘映昆 | Processing reactor of printing and dyeing waste water with catalytic electrode |
| CN108164054B (en) * | 2017-12-30 | 2019-04-12 | 浙江金莱利印染有限公司 | The processing method of dyeing waste water |
| CN110449160B (en) * | 2019-07-30 | 2022-01-11 | 天津大学 | Lanthanum cobaltate-doped material for electrocatalytic purification of organic wastewater and preparation method thereof |
| CN111807478A (en) * | 2020-07-27 | 2020-10-23 | 江苏安凯特科技股份有限公司 | Electrode for electrochemically treating landfill leachate concentrated solution and treatment method |
| CN114836762A (en) * | 2022-04-12 | 2022-08-02 | 西安泰金工业电化学技术有限公司 | Acid treatment process capable of improving durability of titanium electrode |
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