CN1336334A - Diamond coating electrode method for treating hard-to-degrade waste water - Google Patents
Diamond coating electrode method for treating hard-to-degrade waste water Download PDFInfo
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- CN1336334A CN1336334A CN 01126814 CN01126814A CN1336334A CN 1336334 A CN1336334 A CN 1336334A CN 01126814 CN01126814 CN 01126814 CN 01126814 A CN01126814 A CN 01126814A CN 1336334 A CN1336334 A CN 1336334A
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- electrode
- diamond coating
- waste water
- coating electrode
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
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- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
In the technology of treating difficult degradable waste water using diamond coated electrode adopted is CVD boron blended diamond coated electrode having excellent behavious and broader potential window as cathode or anode of electrolysis of waste water treatment, the electrodes are parallel to each other and vertically set in electrolytic bath, solid catalyst is placed in electrolytic bath and electrolyte is added into the solution to raise current efficiency and conductivity. In the present invention used is polished silicone sheet as liner of common boron blended diamond coating electrode or metal tungsten, silicon carbide as liner of nm boron blended diamond coating electrode. Advantages low energy consumption, long electrode service life, broad application range etc.
Description
Technical field:
The present invention relates to a kind of technology, utilize the high-performance of diamond coating electrode material and wide characteristics such as potential window, adopt the male or female of diamond coating electrode as electrolysis treatment waste water with diamond coating electrode processing used water difficult to degradate.Belong to environmental technology and electrochemical field.
Background technology:
Electrochemical method is administered sewage and is had pharmaceutical chemicalss such as need not adding oxygenant, flocculation agent, and equipment volume is little, and floor space is few, advantages such as convenient and flexible operation.But there is anode loss always in electrochemical method, analyses the shortcoming of side reactions such as oxygen liberation of hydrogen, and this has limited the practical ranges of electrolysis treatment waste water greatly.
As everyone knows, diamond has excellent physics, chemical property, so with the anti-poisoning of the electrode of diamond coating, resistant to pollution very capable, can be in the medium-term and long-term stable work of the medium of deep-etching, the distinctive biologically inert of diamond surface makes it be particularly suitable for the processing of the sanitary sewage of biologically active simultaneously; The potential window of diamond coating electrode in the aqueous solution is wide to be reached more than the 3V, has higher overpotential for oxygen evolution than GC electrode, HOPG electrode and metal electrode, the high efficiency generation OH of energy under identical current density, thereby the free-radical oxidn that makes organism be had strong oxidizing property apace is difficult to handle the poison sewage that contains stable performances such as aromatic group so can be used for handling general electrode better; Diamond has high rigidity and high strength, and the high-amplitude wave that can stand ultrasonic cavitation effect counter electrode surface impacts.This impact pressure can be up to 100 normal atmosphere, thereby, long with the electrode life of coated with CVD (chemical vapor deposition) diamond.Make on the basis of conductive semiconductor coating in solution CVD boron-doping technology, external having diamond electrode as electroanalytical chemistry (J.Electroanalytical Chemistry, 473 (1999): 179～185), the high boron-doped diamond electrode of uses such as A.Fujishima is made anode, in the presence of vitamins C, measure Dopamine HCL and NADH, obtain good result.But diamond electrode is used for the research of used water difficult to degradate not to appear in the newspapers as yet.
Summary of the invention:
The present invention is directed to the deficiencies in the prior art, provide a kind of diamond coating electrode to handle the novel process of used water difficult to degradate, utilize the high-performance and the characteristics of diamond coating electrode material, the solvability and the liberation of hydrogen that overcome general anode electrode are analysed the oxygen side reaction, thereby the new electrolysis process of the industrial wastewater treatment of a kind of long lifetime, less energy-consumption, applied range is provided.
The present invention adopts the male or female of diamond coating electrode as electrolysis treatment waste water, selects for use with the polished silicon slice to be the common b-doped diamond film electrode of substrate and to be the nano boron-doped diamond coating electrode of substrate with tungsten (W) and silicon carbide (SiC).Potential window is between 3.54V～3.96V.
The electrolyzer horizontal positioned, CVD b-doped diamond film electrode and another working electrode such as the ferroelectric utmost point, platinum electrode or CVD b-doped diamond film electrode etc. are parallel to each other, two electrodes vertically place electrolyzer, also can adopt multi-group electrode with serial or parallel connection mode layout, thereby increase the processing power of device.Spread the thick solid catalyst of 2-5cm (as gac) in the electrolyzer, it is polarized between two working electrodes, form group's electrode microbattery, thereby improve current efficiency.For improving electroconductibility, can add the 1.0g/L ionogen in the solution, as anhydrous sodium sulphate.Adopt applying direct current in the electrochemical treatment, current density is controlled at 0.006～8A/cm
2(current density excessive or too small all can influence treatment effect).Treatment time is 2 hours, and sampling analysis in different time is surveyed absorbancy at visible region maximum absorption band place respectively, asks chroma removal rate mean value, and measures the chroma removal rate and the COD of each reaction times section
CrChange.
The used diamond coating electrode of the present invention is a kind of electrode materials of new superior performance.This electrode has weather resistance to chemistry, machinery and heat under high electric load, do not have obvious corrosion.Compare with the carbon dioxide process carbon electrode of routine, at 0.006-8Acm
2After energising 1800 hours, electrode electroactive still constant.Diamond coating electrode has high overvoltage to water electrolysis in addition, do not resemble and just beginning to take place redox reaction than the low potential lower surface the glass-carbon electrode, potential window is wide, can directly aromatic group in the dye molecule or the prussiate in the waste water be converted into CO under higher current potential
2, or produce OH and make dye molecule be polymerized to hydrophobic macromole from water, to separate out.The present invention has utilized these character of diamond coating electrode, has satisfied the demand of electrochemical process processing waste water.The diamond coating electrode of multiple shapes such as plane or cylinder is made in employing, can be fit to the processing needs of big trade effluent.
The specific embodiment:
Embodiment 1
It is useless that common diamond coating electrode (substrate is silicon chip) is used for reactive brilliant blue (X-BR) simulation printing and dyeing The processing of water 1, the mensuration of common diamond coating electrode potential window Oxygen anodic evolution voltage (V): 1.61; Cathode hydrogen evolution voltage (V): 1.99; Potential window (V): 3.60 2, common diamond coating electrode is simulated dyeing waste water for the treatment of X-BR
With the anode of common diamond coating electrode as electrochemical treatments, iron plate is negative electrode, interelectrode distance Be 4cm. As simulated wastewater, adding simultaneously 1.0g/L does not have with the reactive brilliant blue (X-BR) of 100mg/L Aqueous sodium persulfate makes simulated wastewater have certain electric conductivity. In electrolytic cell, add the thick graininess of 3.0cm Activated carbon (fully soak with simulated wastewater before using, make it reach adsorption equilibrium) is made catalyst. The control electricity Current density is 0.6A/cm2, the processing time is 2 hours, sample analysis in different time is surveyed absorbance at visible region maximum absorption band place respectively, asks chroma removal rate mean value, and measures the COD of each reaction time sectionCrChange. Result shows that it is useless to process reactive brilliant blue simulation printing and dyeing with common diamond coating electrode Water, after 2 hours, chroma removal rate can reach 99.52%, CODCrClearance is 82.15%. Treatment effect Better.
In the process of electrolysis, obvious Bubble formation is not all arranged on negative electrode, the anode, common diamond is described The potential window of membrane electrode is wider, and behind the use 1800h, electrode surface does not have significant change, can satisfy examination Test requirement, save the energy.
Embodiment 2
Nano diamond coating electrode (substrate is W) is used for direct pink (12B) simulation dyeing waste water. 1, the mensuration of nano diamond coating electrode (substrate is metal w) potential window
Oxygen anodic evolution voltage (V): 2.24; Cathode hydrogen evolution voltage (V): 1.45; Potential window (V): 3.69 2, test
The substrate part of nano diamond coating electrode is coated with envelope with paraffin, as the anode of electrochemical treatments, Iron plate is negative electrode, and interelectrode distance is 4cm. Direct pink (12B) with 100mg/L is useless as simulation Water adds the 1.0g/L anhydrous sodium sulfate simultaneously, makes simulated wastewater have certain electric conductivity. In electrolytic cell (fully soak with simulated wastewater before using, it is flat to make it reach absorption to add the thick granule activated carbon of 3.0cm Weighing apparatus) makes catalyst. The control current density is 1.0A/cm2, the processing time is 2 hours, sample analysis in different time is surveyed absorbance at visible region maximum absorption band place respectively, asks chroma removal rate mean value, and measures the COD of each reaction time sectionCrChange. Result shows, processes with the nano diamond coating electrode Direct pink (12B) simulation dyeing waste water is after 2 hours, chroma removal rate is 94.94%,, CODCrGo Except rate is 80.30%, the result is more satisfied.
In the process of electrolysis, obvious Bubble formation is not all arranged on negative electrode, the anode, this nm of gold is described The potential window of hard rock coated electrode is wider, can satisfy test requirements document, saves the energy.
Embodiment 3
Nano diamond coating electrode (substrate is SiC) is processed the mensuration of certain factory's actual dying 1, nano diamond coating electrode (substrate is SiC) potential window
Oxygen anodic evolution voltage (V): 2.16; Cathode hydrogen evolution voltage (V): 1.38; Potential window (V): 3.54
The substrate part of nano diamond coating electrode is coated with envelope with paraffin, as the anode of electrochemical treatments, Iron plate is negative electrode, and interelectrode distance is 4cm. Adding the thick granule activated carbon of 2.5cm in electrolytic cell (makes Fully soak with simulated wastewater with front, make it reach adsorption equilibrium) make catalyst. The control current density is 0.8A/cm2, other treatment steps are all with embodiment 1. After 2 hours, result is chroma removal rate Can reach 60.45%, CODCrClearance is 86.28%. Treatment effect is better, and electrode uses after three months still Have no loss, as seen its good stability.
Embodiment 4
Common diamond coating electrode (substrate is silicon chip) is processed black liquid
Operating process and condition such as embodiment 1. Waste water adopts through going out after electrodialysis and the active sludge treatment Water (being to be difficult to biodegradable waste water), after dilution, CODCrBe 1360mg/L, 300 times of colourities. Through 2 hours electrolytic treatments, COD was down to 142mg/L, and colourity is 10 times, is close to water white transparency, says The processing of bright this electrode pair hardly degraded organic substance is resultful.
Claims (3)
1, a kind of diamond coating electrode is handled the technology of used water difficult to degradate, it is characterized in that adopting the male or female of the CVD b-doped diamond film electrode of potential window between 3.54V～3.96V as electrolysis treatment waste water, the electrolyzer horizontal positioned, diamond coating electrode and another working electrode are parallel to each other, two electrodes vertically place electrolyzer, spread the thick solid catalyst of 2-5cm in the electrolyzer, add the 1.0g/L ionogen in the solution, the current density of applying direct current is controlled at 0.006～8A/cm
2, the treatment time is 2 hours.
2, handle the technology of used water difficult to degradate as the said diamond coating electrode of claim 1, it is characterized in that said another working electrode is the ferroelectric utmost point, platinum electrode or CVD b-doped diamond film electrode.
3, handle the technology of used water difficult to degradate as claim 1 or 2 said diamond coating electrodes, it is characterized in that said CVD b-doped diamond film electrode is selected for use with the polished silicon slice and be the common b-doped diamond film electrode of substrate or be the nano boron-doped diamond coating electrode of substrate with tungsten, silicon carbide.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB01126814XA CN1140463C (en) | 2001-09-20 | 2001-09-20 | Diamond coating electrode method for treating hard-to-degrade waste water |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB01126814XA CN1140463C (en) | 2001-09-20 | 2001-09-20 | Diamond coating electrode method for treating hard-to-degrade waste water |
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| CN1336334A true CN1336334A (en) | 2002-02-20 |
| CN1140463C CN1140463C (en) | 2004-03-03 |
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| CNB01126814XA Expired - Fee Related CN1140463C (en) | 2001-09-20 | 2001-09-20 | Diamond coating electrode method for treating hard-to-degrade waste water |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303254C (en) * | 2004-04-16 | 2007-03-07 | 清华大学 | Electrobath for treating sewerage |
| CN100591630C (en) * | 2008-04-09 | 2010-02-24 | 江阴顶立环保科技有限公司 | Monocrystalline silicon or carbon-base monocrystalline silicon electrode electrolysis oxidation treatment method for organic chemical sewage |
| CN101798160A (en) * | 2010-04-07 | 2010-08-11 | 东南大学 | Treatment device and pretreatment method of wastewater generated by producing acrylic fibers by using dry method |
| CN102520042A (en) * | 2011-12-19 | 2012-06-27 | 天津理工大学 | Method for preparing boron-doped diamond film electrode for detecting dopamine |
| CN101090870B (en) * | 2004-10-18 | 2013-05-08 | 德诺拉工业有限公司 | Improved COD abatement process for electrochemical oxidation |
| CN103282551A (en) * | 2010-10-14 | 2013-09-04 | 六号元素有限公司 | A bipolar cell for a reactor |
| CN106006850A (en) * | 2016-05-25 | 2016-10-12 | 安徽普氏生态环境工程有限公司 | Method for performing electrochemical oxidative degradation on sewage COD (chemical oxygen demand) by using boron-doped graphene electrode |
| CN108408848A (en) * | 2018-05-10 | 2018-08-17 | 深圳先进技术研究院 | Boron-doped diamond/graphite combination electrode and preparation method, double cell reactor |
| CN111485223A (en) * | 2020-05-11 | 2020-08-04 | 南京岱蒙特科技有限公司 | Boron-doped diamond electrode with ultrahigh specific surface area and preparation method and application thereof |
-
2001
- 2001-09-20 CN CNB01126814XA patent/CN1140463C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303254C (en) * | 2004-04-16 | 2007-03-07 | 清华大学 | Electrobath for treating sewerage |
| CN101090870B (en) * | 2004-10-18 | 2013-05-08 | 德诺拉工业有限公司 | Improved COD abatement process for electrochemical oxidation |
| CN100591630C (en) * | 2008-04-09 | 2010-02-24 | 江阴顶立环保科技有限公司 | Monocrystalline silicon or carbon-base monocrystalline silicon electrode electrolysis oxidation treatment method for organic chemical sewage |
| CN101798160A (en) * | 2010-04-07 | 2010-08-11 | 东南大学 | Treatment device and pretreatment method of wastewater generated by producing acrylic fibers by using dry method |
| CN103282551A (en) * | 2010-10-14 | 2013-09-04 | 六号元素有限公司 | A bipolar cell for a reactor |
| CN103282551B (en) * | 2010-10-14 | 2017-03-22 | 六号元素技术有限公司 | A bipolar cell for a reactor |
| CN102520042A (en) * | 2011-12-19 | 2012-06-27 | 天津理工大学 | Method for preparing boron-doped diamond film electrode for detecting dopamine |
| CN102520042B (en) * | 2011-12-19 | 2014-01-08 | 天津理工大学 | Method for preparing boron-doped diamond film electrode for detecting dopamine |
| CN106006850A (en) * | 2016-05-25 | 2016-10-12 | 安徽普氏生态环境工程有限公司 | Method for performing electrochemical oxidative degradation on sewage COD (chemical oxygen demand) by using boron-doped graphene electrode |
| CN108408848A (en) * | 2018-05-10 | 2018-08-17 | 深圳先进技术研究院 | Boron-doped diamond/graphite combination electrode and preparation method, double cell reactor |
| CN111485223A (en) * | 2020-05-11 | 2020-08-04 | 南京岱蒙特科技有限公司 | Boron-doped diamond electrode with ultrahigh specific surface area and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1140463C (en) | 2004-03-03 |
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