CN1353088A - Electrochemical process for treating waste dye liquid - Google Patents
Electrochemical process for treating waste dye liquid Download PDFInfo
- Publication number
- CN1353088A CN1353088A CN 00133496 CN00133496A CN1353088A CN 1353088 A CN1353088 A CN 1353088A CN 00133496 CN00133496 CN 00133496 CN 00133496 A CN00133496 A CN 00133496A CN 1353088 A CN1353088 A CN 1353088A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- dye wastewater
- electrolysis
- cathode
- wastewater according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
An electrochemical process for treating dye sewage includes such steps as providing a set of electrolysis equipment composed of electrolyzer, electrolysis equipment with cathode and anode, and anode material containing Fe or Cu; adding the said dye sewage and supporting electrolyte to contain 5-20 g/L, turning on electrolysis equipment to start operation, electrolyzing while introducing air to cathode, filtering the electrolyte and collecting the filter matter.
Description
The invention relates to an electrochemical treatment method of dye wastewater.
The waste water treatment of dye and printing and dyeing industry is a puzzling subject, the waste water has large chroma, complex composition and many components which are difficult to biodegrade, in recent years, the report that hydroxyl free radical (namely Fenton reagent) is generated by the reaction of hydrogen peroxide and ferrous ions for treating dye waste water is provided, the Fenton reagent has high oxidation potential (2.8V) and is effective for decoloring and degrading dye, but the cost is high because hydrogen peroxide and ferrous sulfate are added on site, and the industrial application is difficult.
The invention aims to overcome the defects in the prior art and provides the electrochemical treatment method of the dye wastewater, which has simple and easy operation procedure and lower treatment cost and is suitable for industrial application.
The object of the present invention is achieved by the following means.
The electrochemical treatment method of the dye wastewater comprises the following steps:
1. providing a set of electrolysis equipment comprising an electrolysis bath, a cathode and an anode,
1.1 anode material: either pure metallic iron, or an iron alloy, or pure metallic copper, or a copper alloy,
1.2 adding dye wastewater and supporting electrolyte into the electrolytic bath to form electrolyte, and leading the content of the supporting electrolyte in the electrolyte to be 5-20g/L,
1.3 electrifying the electrolytic cell for electrolysis, introducing oxygen into the cathode during electrolysis,
1.4 filtering the electrolyte and collecting the filtrate.
The anode, which is either an iron electrode or a copper electrode, plays the same role in the present invention, and the following description of the reaction mechanism is made by taking an example of an iron electrode, and all the following descriptions regarding "iron" are equally applicable to "copper".
When energized, the same electrochemical equivalent of electrochemical reaction will occur on the anode and cathode, since the Fe on the anode0→Fe2+And on the cathode from O2→H2O2All the reactions in (2) are two-electron reactions, so that the same molar amount of Fe will be generated in the electrolytic cell in the same time2+And H2O2Thereby enabling the subsequent Fenton reagent-forming chemical reaction to be carried out.
The specific reaction mechanism is as follows: after the electrification, the ferrous ions dissolved from the anode react with the hydrogen peroxide generated on the cathode to generate hydroxyl radicals with extremely high oxidation potential (2.8V), although the existence time of the hydroxyl radicals is extremely short (less than 10 percent)10+Second), but it has a very strong oxidizing power, so that the chromophoric group of the organic solvent can be destroyed and decolorized. It is known that amines and phenols have a high redox potential, around 0.6-0.8V, and sulfonic acids have a redox potential around 0.3-0.8V, both of which are considerably lower than the oxidation potential of Fenton's reagent, in other words, Fenton's reagent is sufficient to oxidize the unsaturated double bonds in these dye groups, giving rise to degradation and discoloration effects. The ferric ions generated in the reaction will combine with hydroxide ions in the solution to generate flocculent Fe (OH)3，Fe(OH)3Co-depositing the coated organic substances, filtering, and collecting the filter residuePart of Fe generated in Fenton reaction is removed3+Electrode cycling between divalent and trivalent ions can be performed according to equation (1). The overall reaction can therefore be described as an electrochemical subsequent (EC) reaction. The reaction of organic matter on the electrode is led to the solution for long time, and the voltage in the electrolyzer is always maintained constant.
Oxygen is bubbled into the cathode during electrolysis and may be changed to air-bubbled into the cathode during specific operations, and therefore this definition in the claims shall include "air-bubbled".
Different reactions occur at the cathode when oxygen is introduced and when oxygen is not introduced, only reaction (1), namely Fe, occurs at the electrode3+Reduction to Fe at the electrode2+The concentration of the trivalent iron ion generated in the solution is small, and the concentration polarization is large, so that the electrode potential is increased, while in the present invention, O is introduced2Thus, the reaction of equation (2) to generate hydrogen peroxide occurs, and the electrode potential can be maintained at a low level.
The object of the present invention can also be achieved by the following means.
The method also comprises the following step of stirring the electrolyte during electrolysis.
The method also comprises the following step of introducing air while stirring the electrolyte during electrolysis.
The solution in the electrolytic tank is stirred, so that the Fe generated by the cathode and the anode can be reduced2+And H2O2The concentration polarization in the transmission process in the solution promotes the movement of the electrolyte and reduces the resistance.
The current density of the anode electrolysis is 4-10mA/cm2The cathode electrolytic current density is 4-13mA/cm2。
During electrolysis, the cathode and the anode are easy to generate side reaction of hydrogen and oxygen evolution, and the reaction formula is as follows:
the occurrence of side reactions leads to the loss of electrolysis and must be avoided, and experimental data shows that the voltage of the electrolytic bath has a trend of increasing linearly with the increase of current density.
Electrically depositing on the cathode2Since the reaction of reducing the hydrogen peroxide is carried out, the electrode potential can be kept low as long as the reaction is controlled within a range in which hydrogen is not evolved. Another experimental data shows that when the current density is less than 10mA/cm2In this case, the electrode potential of the cathode is low, and hydrogen gas is not generated. The cell voltage corresponding to the current density is below 5V, while the cell voltage of the electrochemical method in the prior art is about 15V, so the energy consumption of the electrochemical method is lower than that of the conventional electrochemical method.
Similarly, when the current density of the anode is less than 10mA/cm2In this case, no oxygen is generated.
Further comprises the following steps that the electrolytic bath is irradiated by ultraviolet lamp light with the wavelength of 240-280nm during electrolysis.
Under the irradiation of ultraviolet light, the degradation of industrial dye wastewater can be accelerated, and the decolorizing effect is enhanced.
The anode material is a pure metallic iron.
The anode configuration is either flat or grid-like.
The cathode material is either a graphite, a pure titanium, or a titanium alloy.
The cathode is in a flat plate shape, or is a columnar porous electrode, or is in a grid shape.
By adopting the electrodes with different configurations, the effect of reducing the cell voltage can be achieved by reducing the current density of the electrodes to a certain extent.
The supporting electrolyte is either sodium sulfate, potassium sulfate, or potassium hydroxide.
The pH of the electrolyte is preferably in the range of 4 to 10.
Since the conductivity of organic waste water solutions is very poor, the addition of a suitable supporting electrolyte is necessary for the operation of the electrolysis cell. Although many soluble inorganic electrolytes can be found, chloride and nitrate salts are not suitable because they generate irritating chlorine gas or various toxic and harmful nitride gases at the anode during electrolysis.
KOH, NaOH solutions have a low specific resistance even at low concentrations, but because oxygen (O) will be present in the cell2) The reduction to hydrogen peroxide, as shown in equation 2, must be carried out in an acidic or neutral solution, and therefore, a sodium sulfate solution is more suitable. Although the specific resistance of the sodium sulfate solution is much greater than that of the KOH solution, the conductivity of the sodium nitrate solution increases rapidly with increasing concentration, and the conductivity of the solution is always stable because it does not participate in the electrolytic reaction.
In summary, compared with the prior art, the invention has the following advantages: the method is simple and easy to implement, has low equipment investment, simple operation and low energy consumption in the treatment process, has high effect on decoloring and degrading the dye, and is suitable for industrial application.
The present invention will be described in more detailwith reference to the following examples.
Example 1:
the electrochemical treatment method of the dye wastewater comprises the following steps:
1. providing a set of electrolysis equipment comprising an electrolysis bath, a cathode and an anode,
1.1 the cathode is a graphite plate,
1.2 the anode is an iron plate,
2. adding dye wastewater and potassium sulfate into the electrolytic bath to form electrolyte, wherein the content of the potassium sulfate in the electrolyte is 5g/L,
3. electrifying the electrolytic bath for electrolysis,
3.1 anodic electrolytic CurrentThe density was 4mA/cm2。
3.2 cathode Electrolysis Current Density of 4mA/cm2。
4. During electrolysis
4.1 oxygen sparging into the cathode
4.2 stirring the electrolyte
5. The electrolysis time is 1.5 hours,
6. filtering the electrolyte and collecting the filtrate, wherein the obtained filtrate is water for discharge.
Table 1:
| wavelength of light (nm) | 0.0h | 0.5h | 1.0h | 1.5h |
| 350 | 1.102 | 0.134 | 0.208 | 0.06 |
| 400 | 0.688 | 0.073 | 0.078 | 0.02 |
| 450 | 0.496 | 0.048 | 0.045 | 0.011 |
| 500 | 0.378 | 0.032 | 0.029 | 0.006 |
| 550 | 0.298 | 0.019 | 0.019 | 0.003 |
| 600 | 0.240 | 0.015 | 0.015 | 0.002 |
| 650 | 0.206 | 0.011 | 0.013 | 0.00 |
| 700 | 0.203 | 0.013 | 0.016 | 0.00 |
Table 1 shows the change of the absorption intensity of visible light in the wavelength range of visible light of 350-700nm after the wastewater from Fuhua printing and dyeing mill and the electrolysis treatment thereof. The printing and dyeing wastewater discharged by Fuhua printing and dyeing factories is about 200 cubic meters every day, and the discharged wastewater is absorbed at each visible light wavelength. After the treatment for 1.5 hours by the electrolytic bath, the absorption intensity of the wave length above 500nm is basically close to zero, and the absorption intensity of the wave length above 350-500nm is reduced by more than 90 percent. It can also be seen from the table that the decrease in the absorption intensity in the first half hour of the electrolysis treatment was as high as 90%, and the change in the latter half hour appeared to be insignificant, where the electrolyte was brown, as judged from the color of the electrolyte, where there was a significant amount of Fe (OH) in the cell3The chromophoric groups of many organic dyes, such as 1, 5-naphthalene diamine, 1-aminophenyl trisphenol, 1-naphthylamine-6 sulfonic acid, etc., combine with ferric iron in alkaline solution to form blue macromolecular complexes, so that we have reason to deduce blue color according to the change of solution colorThe same course is also experienced in the cell at this time. It appears that the entire degradation decolorization reaction can be divided into two steps: firstly, electrochemical degradation decolorization is carried out under the action of free hydroxyl, and then the codeposition process of iron hydroxide coated macromolecular complexes is carried out.
The best embodiment is as follows:
the electrochemical treatment method of the dye wastewater comprises the following steps:
1. an electrolysis apparatus is provided comprising an electrolysis cell, a cathode and an anode.
1.1 the anode is in a grid shape and made of ferroalloy.
1.2 the cathode is a columnar porous electrode made of titanium alloy.
2. Adding dye wastewater and sodium sulfate into an electrolytic cell to form electrolyte, wherein the content of the sodium sulfate in the electrolyte is 20g/L,
3. electrifying the electrolytic bath for electrolysis,
3.1 Anode electrolytic Current Density of 10mA/cm2
3.2 cathode Electrolysis Current Density of 10mA/cm2
4. During electrolysis
4.1 blowing air to the cathodes
4.2 stirring the electrolyte and blowing air
4.3 the electrolytic bath is irradiated by ultraviolet lamp with the wavelength of 240-280nm,
5. the electrolysis time was 2 hours
6. Filtering the electrolyte and collecting the filtrate to obtain the filtrate which is the water for discharging.
The printing and dyeing wastewater discharged by Fuhua printing and dyeing mills is about 2000 cubic meters every day, and as can be seen from Table 1, the discharged wastewater is absorbed at each visible light wavelength. After 2 hours of the electrolytic treatment, the absorption at all visible wavelengths disappeared, and the filtrate was colorless and transparent, and it can be seen from the table that the absorption intensity decreased up to 90% in the first half hour of the electrolytic treatment.
TABLE 1 variation of the absorption intensity of visible light with time
Table 2: treatment results of 2L of industrial dye wastewater under different currents
| Wavelength of light (nm) | 0.0h | 0.5h | 1.0h | 2h |
| 350 | 1.102 | 0.134 | 0.208 | 0.047 |
| 400 | 0.688 | 0.073 | 0.078 | 0.0092 |
| 450 | 0.496 | 0.048 | 0.045 | 0.00 |
| 500 | 0.378 | 0.032 | 0.029 | 0.00 |
| 550 | 0.298 | 0.019 | 0.019 | 0.00 |
| 600 | 0.240 | 0.015 | 0.015 | 0.00 |
| 650 | 0.206 | 0.011 | 0.013 | 0.00 |
| 700 | 0.203 | 0.013 | 0.016 | 0.00 |
| COD removal Rate (%) | ||||||
| Current (A) | Voltage (volt) | 15 minutes | 0.5 hour | 1 hour | 1.5 hours | 2 hours |
| 0.5 | 2 | 49.4 | 61.6 | 69.9 | 71.1 | - |
| 0.75 | 4 | 68.0 | 67.9 | 72.1 | 73.0 | 73.5 |
| 1 | 6 | 68.8 | 73.7 | 74.7 | 74.7 | 78.5 |
| 1.25 | 9 | 81.7 | 82.1 | 81.9 | 84.2 | 83.8 |
Claims (10)
1. The electrochemical treatment method of the dye wastewater is characterized by comprising the following steps:
1.1 providing a set of electrolysis apparatus comprising an electrolysis cell, a cathode and an anode
1.1.1 anode materials: either pure metallic iron, or an iron alloy, or pure metallic copper, or a copper alloy,
1.2 adding dye wastewater and supporting electrolyte into the electrolytic bath to form electrolyte, and leading the content of the supporting electrolyte in the electrolyte to be 5-20g/L,
1.3 electrifying the electrolytic cell for electrolysis, introducing oxygen into the cathode during electrolysis,
1.4 filtering the electrolyte and collecting the filtrate.
2. The method for electrochemically treating dye wastewater according to claim 1, further comprising stirring the electrolyte during electrolysis.
3. The method for electrochemically treating dye wastewater according to claim 1, further comprising introducing air while stirring the electrolyte during electrolysis.
4. The method for electrochemically treating dye wastewater according to claim 1, wherein the anodic electrolysis current density is 4 to 10mA/cm2The cathode electrolytic current density is 4-13mA/cm2。
5. The method for electrochemically treating dye wastewater according to claim 1, further comprising the step of irradiating the inside of the electrolytic cell with ultraviolet light having a wavelength of 240-280nm during electrolysis.
6. The method for electrochemically treating dye wastewater according to claim 1, wherein the anode material is a pure metallic iron.
7. The method for electrochemically treating dye wastewater according to claim 1 or 6, wherein the anode is configured in either a flat plate shape or a mesh shape.
8. The method of claim 1, wherein the cathode material is either graphite, pure titanium or a titanium alloy.
9. The method for electrochemically treating dye wastewater according to claim 1 or 8, wherein the cathode is configured as a porous electrode having either a flat plate shape or a columnar shape.
10. The method for electrochemically treating dye wastewater according to claim 1, wherein the supporting electrolyte is either sodium sulfate, potassium sulfate, or potassium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001334964A CN1140461C (en) | 2000-11-09 | 2000-11-09 | Electrochemical process for treating waste dye liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001334964A CN1140461C (en) | 2000-11-09 | 2000-11-09 | Electrochemical process for treating waste dye liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1353088A true CN1353088A (en) | 2002-06-12 |
| CN1140461C CN1140461C (en) | 2004-03-03 |
Family
ID=4595756
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001334964A Expired - Fee Related CN1140461C (en) | 2000-11-09 | 2000-11-09 | Electrochemical process for treating waste dye liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1140461C (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100400433C (en) * | 2005-08-16 | 2008-07-09 | 同济大学 | Strengthened primary treatment method for internal electrolyzing sewage through aeration and catalyzing iron |
| CN101638257B (en) * | 2009-07-17 | 2011-07-20 | 东北大学 | Method and device for treating dye wastewater employing periodic reverse electrocoagulation |
| CN102225797A (en) * | 2011-04-20 | 2011-10-26 | 上海电力学院 | Rare earth doped Ti-based manganese dioxide electrode and preparation method thereof |
| CN102229442A (en) * | 2011-04-20 | 2011-11-02 | 上海电力学院 | Method for treating printing and dyeing wastewater with rare earth cerium doped titanium-based manganese dioxide electrode |
| CN102381744A (en) * | 2011-09-28 | 2012-03-21 | 天津市环境保护科学研究院 | Polyphase multipole electrocatalytic industrial wastewater processing system for high efficiency biological toxicity removal |
| CN106430430A (en) * | 2015-08-11 | 2017-02-22 | 山东卓展环保科技有限公司 | Electrochemical sewage treatment system and sewage treatment method thereof |
| CN108017118A (en) * | 2017-06-15 | 2018-05-11 | 武汉科技大学 | A kind of method based on electrochemical modification method processing cationic dyes waste water |
| CN108164060A (en) * | 2018-01-31 | 2018-06-15 | 常州市武进天工机械制造有限公司 | A kind of printing and dyeing secondary settlement waste water treatment process |
| CN109399765A (en) * | 2017-08-16 | 2019-03-01 | 南京理工大学 | Utilize the method for amorphous alloy electrochemical degradation azo dyes |
| CN111573775A (en) * | 2020-06-19 | 2020-08-25 | 西安工业大学 | Method for photoelectrochemical degradation of rhodamine B |
-
2000
- 2000-11-09 CN CNB001334964A patent/CN1140461C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100400433C (en) * | 2005-08-16 | 2008-07-09 | 同济大学 | Strengthened primary treatment method for internal electrolyzing sewage through aeration and catalyzing iron |
| CN101638257B (en) * | 2009-07-17 | 2011-07-20 | 东北大学 | Method and device for treating dye wastewater employing periodic reverse electrocoagulation |
| CN102225797B (en) * | 2011-04-20 | 2013-04-10 | 上海电力学院 | Rare earth doped Ti-based manganese dioxide electrode and preparation method thereof |
| CN102229442A (en) * | 2011-04-20 | 2011-11-02 | 上海电力学院 | Method for treating printing and dyeing wastewater with rare earth cerium doped titanium-based manganese dioxide electrode |
| CN102229442B (en) * | 2011-04-20 | 2013-04-10 | 上海电力学院 | Method for treating printing and dyeing wastewater with rare earth cerium doped titanium-based manganese dioxide electrode |
| CN102225797A (en) * | 2011-04-20 | 2011-10-26 | 上海电力学院 | Rare earth doped Ti-based manganese dioxide electrode and preparation method thereof |
| CN102381744A (en) * | 2011-09-28 | 2012-03-21 | 天津市环境保护科学研究院 | Polyphase multipole electrocatalytic industrial wastewater processing system for high efficiency biological toxicity removal |
| CN102381744B (en) * | 2011-09-28 | 2013-11-27 | 天津市环境保护科学研究院 | Polyphase multipole electrocatalytic industrial wastewater processing system for high efficiency biological toxicity removal |
| CN106430430A (en) * | 2015-08-11 | 2017-02-22 | 山东卓展环保科技有限公司 | Electrochemical sewage treatment system and sewage treatment method thereof |
| CN108017118A (en) * | 2017-06-15 | 2018-05-11 | 武汉科技大学 | A kind of method based on electrochemical modification method processing cationic dyes waste water |
| CN109399765A (en) * | 2017-08-16 | 2019-03-01 | 南京理工大学 | Utilize the method for amorphous alloy electrochemical degradation azo dyes |
| CN108164060A (en) * | 2018-01-31 | 2018-06-15 | 常州市武进天工机械制造有限公司 | A kind of printing and dyeing secondary settlement waste water treatment process |
| CN111573775A (en) * | 2020-06-19 | 2020-08-25 | 西安工业大学 | Method for photoelectrochemical degradation of rhodamine B |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1140461C (en) | 2004-03-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108726640B (en) | Method for removing organic pollutants in wastewater by electrochemical cooperation with persulfate | |
| CN107129011B (en) | Device and method for treating high-chloride organic wastewater through electrolysis-ionic membrane coupling | |
| CN102101733B (en) | Method for treating electroplating comprehensive wastewater by scrap iron electrolysis and electrochemical technology | |
| CN1850643A (en) | Method for degrading aminobenzene or/and nitrobenzene in waste water by electrolytic process | |
| DE10216860A1 (en) | Electrolysis cell manufacturing hydrogen peroxide is fed with air and low concentration solution of salts | |
| CN1789150A (en) | Method and apparatus for highly efficient removal of water organisms by utilizing photoelectric Fenton reaction | |
| CN104386784B (en) | A kind of load iron ionic activity Carbon fibe composite cathode, preparation method and application thereof | |
| CN1247467C (en) | Technique of electrolytic oxidation for treating waste water of containing phenol | |
| CN113929187B (en) | Anode electrochemical oxidation water treatment method by coupling active chlorine with hydroxyl radical | |
| CN100366545C (en) | Method and apparatus for removing water organisms by utilizing inductive electric Fenton reaction | |
| CN1353088A (en) | Electrochemical process for treating waste dye liquid | |
| CN111252963A (en) | Treatment method of high-concentration COD wastewater | |
| CN104140142A (en) | Coupling treatment method for fracturing flow-back fluid | |
| CN113699542A (en) | H2O2Continuous electrochemical synthesis system | |
| CN106830204B (en) | Method and device for degrading pollutants in water by exciting permanganate through electrochemical cathode | |
| CN1884631A (en) | Method and device for cleaning organic matter using electrochemical method | |
| CN113707352A (en) | Method for treating radioactive comprehensive wastewater | |
| CN104229950A (en) | Preparation and application of manganese ion loaded activated carbon fiber composite cathode | |
| CN110872145B (en) | Method for removing organic matters by electrochemical cooperation with hydrogen peroxide | |
| CN112374666B (en) | Three-dimensional electrolytic sewage treatment method | |
| JP2975577B2 (en) | Electrolytic treatment of electroless nickel plating wastewater | |
| Aryanti et al. | The influence of applied current density and agitation speed during electrocoagulation of textile wastewater | |
| CN1629079A (en) | Electrochemical method and apparatus for removing organic substances from water | |
| CN1212981C (en) | Method for treating waste water containing non-ionic surface active agent | |
| JPH07256297A (en) | Purification treatment of livestock excretion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |