CN105036258A - Application method of porous graphite electrode in industrial wastewater treatment - Google Patents
Application method of porous graphite electrode in industrial wastewater treatment Download PDFInfo
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- CN105036258A CN105036258A CN201510569567.5A CN201510569567A CN105036258A CN 105036258 A CN105036258 A CN 105036258A CN 201510569567 A CN201510569567 A CN 201510569567A CN 105036258 A CN105036258 A CN 105036258A
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Abstract
The invention discloses an application method of a porous graphite electrode in industrial wastewater treatment. An electrochemical method is adopted for treating industrial wastewater. According to the method, the porous graphite electrode is adopted as an electrolytic electrode. The porous graphite electrode is cubic and is formed by sintering graphite powder and a binding agent. A plurality of through holes forming honeycombing porosities are formed inside the porous graphite electrode. According to the application method, the problem that the number of iron or aluminum ions in wastewater is increased due to the adoption of an iron or aluminum electrode is solved, meanwhile, the problem of adsorption of organic pollutant generated by an activated carbon electrode is avoided, and the problem of passivation of the metal electrode due to the fact that a large amount of oxygen is generated in the electrolysis process is avoided; meanwhile, due to the fact that the porous graphite electrode has insolubility, the advantage that the electrode has no loss is achieved, the total effect of industrial wastewater treatment through the electrochemical method is improved, secondary pollution is reduced, the cost is lowered, and good conditions are created for reclaimed water reuse through the reverse osmosis process. The application method has the wide application prospect in the industrial wastewater treatment field through the high-frequency high-voltage pulse electrochemical process.
Description
Technical field
The present invention relates to the process of trade effluent, particularly one
the application method of porous graphite electrode in Industrial Wastewater Treatment, belong to environmental technology field.
Background technology
Hf and hv pulse electricity flocculation technology for treating industrial waste water results from the U.S. the earliest, be mainly used in the improvement of hull mud and oily(waste)water, after improving and improving, be applied to again the harmless treatment of the metal ion pollution waste water such as smeltery, Electroplate Factory, domestic beginning in field of industrial waste water treatment applies hf and hv pulse electric flocculation technique at present.What the material of the conductive electrode in existing hf and hv pulse electric flocculation technique adopted is all metallic iron or aluminium, although iron or aluminium matter electrode have draw materials conveniently, the advantage such as intensity is high, good conductivity, and the floss that can produce ferrous iron or aluminium in electrolytic process contributes to better flocculation sediment, but also have its unsurmountable shortcoming:
1, the metal electrode of iron or aluminium can dissolve in electrolytic process, and especially when needs high-voltage reduces some ion time, high-frequency and high-voltage can more violent dissolution of metals electrode more quickly, produces the oxide compound of iron or aluminium in the electrolytic solution.In order to remove these metal oxides, alkaline matter will be added to produce basic metal, it is made to generate the precipitation of hydroxide of metal in the electrolytic solution, mud is commonly called as like this with regard to causing a large amount of chemical precipitates, the waste produced in wastewater treatment process is increased, causes the secondary pollution in water treatment procedure.
2, in the electricity flocculation electrolytic process of hf and hv pulse, because the generation of electrolytic process Anodic a large amount of oxygen on the surface makes the metal electrode of iron or aluminium very easily surface passivation occur, cause the reduction of further electrolytic efficiency, thus affect the effect of wastewater treatment.
3, after objectionable constituent have been processed in trade effluent, in water, a certain amount of iron or aluminum ion can be remained, give and adopt reverse osmosis method to bring larger difficulty to Treated sewage reusing process further.
4, in electricity flocculation electrolytic process, the dissolving of iron or aluminum metal causes a large amount of consumption of electrode matel material, thus makes the wastage rate of metal electrode very high, also just considerably increases the use cost of electrode.
In order to overcome in Industrial Wastewater Treatment the deficiency using the metal electrode such as iron or aluminium, having had the carbon dioxide process carbon electrode that application of pure gac makes and having carried out the example of Industrial Wastewater Treatment, however due to the adsorptive power of gac excessively strong,
gacelectrode can adsorb the organic pollutant produced in a large amount for the treatment of processes in wastewater treatment process, blocks the vesicular structure in gac in the course of time, causes the decline of activated carbon electrodes conductivity, thus greatly reduce the effect of sewage disposal.
Graphite opaque is soft, and black gray expandable has greasy feeling, and hardness is 1 ~ 2, and proportion is 1.9 ~ 2.3; Under the condition of starvation, its fusing point, more than 3000 DEG C, is one of the most resistant to elevated temperatures mineral; Can react with oxygen under different high temperature, generate carbonic acid gas or carbon monoxide; Only have in halogen fluorine can with simple substance carbon direct reaction; In a heated condition, Graphite Powder 99 more easily by acid oxidase, at high temperature, Graphite Powder 99 can also with many metal reactions, generate metallic carbide, may be used for metal smelting.The salient features of graphite is as follows:
Electroconductibility: the electroconductibility of graphite is nonmetal higher 100 times than general.
Thermal conductivity: exceed the metallic substance such as steel, iron, lead, thermal conductivity raises with temperature and reduces, and graphite becomes thermal insulator even at very high temperatures.
Chemical stability: graphite has good chemical stability at normal temperatures, can the corrosion of acidproof, alkaline-resisting and organic solvent-resistant.
Plasticity-: the good toughness of graphite, can be bonded to very thin thin slice.
Because Graphite Powder 99 has above various performances, in electrical industry, be thus widely used as the coating etc. manufacturing brush, carbon-point, carbon pipe, the positive pole of mercuryrectifier, graphite gasket, phone parts and picture tube.
Summary of the invention
Technical problem to be solved by this invention is, overcomes the deficiency using metal electrode or pure activated carbon electrodes in existing hf and hv pulse electricity flocculation process for treating industrial waste water, provides
the application method of porous graphite electrode in Industrial Wastewater Treatmentadopt the porous graphite be made up of Graphite Powder 99 and binding agent as electrolysis electrode, by hf and hv pulse electrochemical process, trade effluent is processed, reach to reduce in electrolytic process and again produce metal ion waste, avoid electrode passivation, reduce export license and stop the effect of the adsorption effect of electrode own, thus improve the processing power of trade effluent, reduce secondary pollution, reduce the use cost of electrode, and create conditions for the Treated sewage reusing process of further reverse osmosis method.
It is as follows that the present invention solves the technical scheme that its technical problem takes:
A kind of
the application method of porous graphite electrode in Industrial Wastewater Treatmentadopt electrochemical process to process trade effluent, it is characterized in that: described method adopts porous graphite electrode as the electrode of electrolysis, and this porous graphite electrode is cubes, sintered by Graphite Powder 99 and binding agent and form, its inside is provided with the some through holes forming cellular porosity.
As further improvement, described porous graphite electrode contains nano-sized carbon.
As further improvement, the mass ratio that described nano-sized carbon accounts for described porous graphite electrode is 5%.
As further improvement, the concrete technology step of described method is as follows:
(1) in electrochemical cell by multiple described porous graphite electrode superposition to form electrolysis electrode, during superposition each porous graphite electrode cubes on through hole interpenetrate or intermesh;
(2) in PH equalizing tank, according to the difference of institute's metal ion and Components of Organic Pollutants in trade effluent and the difference of concentration, the pH value of trade effluent is regulated;
(3) trade effluent regulated through PH is injected electrochemical cell, adopt Industrial Wastewater Treatment power supply to carry out electrolysis to trade effluent energising;
(4) trade effluent after electrolysis enters PH equalizing tank, requires the pH value of the trade effluent after electrolysis to be adjusted to 8-12 according to the difference of various trade effluent;
(5) add flocculation agent in the trade effluent after regulating through PH, accelerate to produce and precipitate and remove throw out;
(6) supernatant water after removing throw out carries out the reprocessing of next technique after filtering or directly discharges.
As further improvement, in described step (2), the pH value of trade effluent is adjusted to 2-12.
As further improvement, in described step (3), the voltage needed for electrolysis, electric current and time determine according to the composition of institute's metal ion and organic pollutant in trade effluent and concentration.
Compared with prior art, the present invention changes the existing way using metal and gac as electrolysis electrode, have employed composition be the electrode of porous graphite as the conductive electrode of power supply in hf and hv pulse electrolytic process, reach following beneficial effect:
1, the secondary pollution of water quality is avoided---the material due to porous graphite electrode is nonmetal instead of the metal such as iron or aluminium, thus can not dissolve in electrolytic process, metallic oxyhydroxide, thus cause a large amount of chemical sludges to produce, therefore in wastewater treatment process, porous graphite electrode can not increase any pollutent, and the secondary pollution of water quality also can not occur.
2, prevent electrode passivation, improve electrolytic efficiency---because porous graphite electrode self does not participate in solubilizing reaction in electrolytic acid cleaning oxydation process, therefore in the electrochemical electrolysis process of hf and hv pulse, a large amount of oxygen that trade effluent is separated out in positive electrode surface by electrolysis can not make porous graphite electrode surface produce zone of oxidation and cause electrode passivation, thus the electrical conductive activities of porous graphite electrode can not be affected, the metal ion be more conducive in trade effluent directly obtains electron reduction or complex compound obtains great amount of hydroxy group polar group in the basic conditions by fully degraded (metal ion is easy to form precipitate metal hydroxides), thus the electrolytic efficiency substantially increased in wastewater treatment process, make the use range of processing method of the present invention more wide in range, more be conducive to adapting to the needs that the redox needs of various different pollutent and high concentration organic contaminant are degraded.
3, be conducive to trade effluent and carry out Treated sewage reusing process---because electrode is not iron or aluminium, so greatly reduce remaining iron or aluminum ions content in water after treatment, therefore enable trade effluent be easier to enter reverse osmosis system and carry out further Treated sewage reusing process.
4, use cost is cheap---and porous graphite electrode, due to the oxidation dissolution on not generating electrodes surface, so can not produce consumption, because this reducing the use cost of electrode, improves the cost performance of electrode.
5, improve the effect of sewage disposal---because porous graphite electrode does not have
activated carbonthe adsorption that electrode has, has stopped the adsorption effect of electrode itself, avoids the decline of electrodes conduct performance, substantially increases the effect of sewage disposal, extends the work-ing life of electrode simultaneously.
6, current consumption is reduced---the resistance adding the Graphite Electrodes of nano-carbon powder has obvious change, resistance not containing the porous graphite electrode of nano-carbon powder is 20-60 ohm/10cm length, the resistance adding the porous graphite electrode of nano-carbon powder can be reduced to 5-20 ohm/10cm length, therefore the porous graphite electrode containing nano-carbon powder obviously can reduce the current consumption of water treatment, reduces the cost of water treatment.
Accompanying drawing explanation
fig. 1it is the structure letter of the porous graphite electrode in the present invention
figure.
fig. 2it is technical process of the present invention
figure.
Embodiment
The present invention is a kind of
novelelectrochemical wastewater treatment method, adopt the porous graphite be made up of Graphite Powder 99 and binding agent as electrolysis electrode, trade effluent is processed by electrochemical process with high-frequency and high-voltage impulse power supply, decrease in original electric flocculation process and adopt iron or aluminium electrode and the increase causing iron or aluminum ion amount in waste water, avoid the electrode passivation caused due to the generation of a large amount of oxygen in electrolytic process, the loss-free beneficial effect of electrode is reached due to the insoluble of porous graphite electrode, stopped the adsorption effect of electrode itself simultaneously, avoid the decline of electrodes conduct performance, substantially increase the effect of sewage disposal, extend the work-ing life of electrode, in addition the porous graphite electrode containing nano-carbon powder obviously can reduce the current consumption of water treatment, reduce the cost of water treatment, thus substantially increase the overall efficacy of Industrial Wastewater Treatment, decrease secondary pollution, and in Treated sewage reusing process, create good condition for reverse osmosis method.
Below in conjunction with case study on implementation and
accompanying drawingthe present invention is described in further detail.
Application method of the present invention adopts electrochemical process to process trade effluent, and the electrode of its electrolysis adopts porous graphite electrode.Refer to
fig. 1,
diagramthe profile of porous graphite electrode is cubes, and its inside is provided with and penetrates cubical some through holes, forms cellular hole.Described porous graphite electrode is sintered by the Graphite Powder 99 conducted electricity and binding agent and forms after mould is molded.Described binding agent is resin or the water glass of conduction, or the binding agent of other conduction.The composition of described porous graphite electrode can also include nano-sized carbon to reduce resistance, and the mass ratio that this nano-sized carbon accounts for described porous graphite electrode can be 5%.
Refer to again
fig. 2, of the present invention
the application method of porous graphite electrode in Industrial Wastewater Treatmentprocessing step as follows:
(1) porous graphite electrode is settled
In electrochemical cell, cubical porous graphite electrode is stacked up to form electrolysis electrode; When superposition is laid, according to technique actual conditions, the through hole on the cubes of each porous graphite electrode can intermesh, and also can interpenetrate, and ensures that each drip fully can both be obtained electrolysis through the trade effluent of electrochemical cell with this; The form stacked can, in skewed, also can be column shape.
(2) pH value of trade effluent is regulated
Measure the pH value of trade effluent, then use the PH auto-controller controlled by sequence control system, in PH equalizing tank, the pH value of trade effluent is adjusted to 2-12; Its concrete adjustable value will be determined according to the difference of the composition of institute's metal ion and organic pollutant in trade effluent and the difference of concentration.
(3) electrochemical electrolysis trade effluent
Trade effluent after PH regulates injects electrochemical cell, adopts high-frequency and high-voltage impulse power supply, carries out energising electrolysis by porous graphite electrode to trade effluent.Voltage and current needed for electrolysis is determined according to the feature of metal cation component contained in trade effluent or organic pollutant, and voltage is generally in the scope of 100-300V, and required electric current is generally between 30-250A.Time of electrochemical electrolysis completely according to needing the composition of metal ion to be processed and concentration in trade effluent, the flow of characteristic sum trade effluent of organic pollutant determines, general control is best at 30-60 minute, and such time controling is adapted at generally using in the trade effluent of large discharge.
(4) pH value of the trade effluent after electrolysis is regulated
Trade effluent after electrolysis enters PH equalizing tank, uses PH auto-controller according to the different requirements of various trade effluent, is regulated within the scope of 8-12 by the pH value of the trade effluent after electrolysis.
(5) flocculation sediment
Regulate in above-mentioned steps (4) in the water of pH value and add a small amount of flocculation agent (such as PAM), enter settling tank after stirring and carry out flocculation sediment.
(6) subsequent disposal
Remove the supernatant water after throw out after filtering, according to circumstances or with Fenton process continue process until qualified discharge, also can enter biochemical treatment tank and continue process qualified discharge.
(7) Treated sewage reusing
Also test reaches the clear water of emission standard after filtration, can enter Revere Osmosis Process System and carry out Treated sewage reusing art breading further.
With embodiment, water treatment efficiency of the present invention is described below.
Embodiment one
Industrial Wastewater Treatment object is plastic electroplating comprehensive wastewater, and before process, in waste water, each ionic concn content is as follows with other index:
Metallic nickel :≤50mg/L, metallic copper :≤100mg/L, chromium metal :≤50mg/L;
COD (chemical oxygen demand (COD)): 400mg/L, PH=2.5, specific conductivity 4000-5000s.
Adopt method of the present invention to process to above-mentioned waste water, in step (2), regulate the pH value to 2 of waste water; In step (3), electrolysis time is 30 minutes, and after electrolysis, water quality PH is 4-5.5; In step (4), regulate the PH=8 of water; Finally by discharge after step (5) and (6) flocculation sediment and filtration.
Described waste water is after with the flocculation process that powers on, and after process, the sampling analysis result of clear water is as follows:
PH=7.5-7.8, specific conductivity=4500s, COD < 80mg/L;
Ionic concn content:
Metallic nickel: 0.28mg/L, metallic copper: 0.32mg/L, chromium metal: 0.11mg/L.
Above analytical results shows, reaches after waste water is processed
countryfirst discharge standard.
Embodiment two
Industrial Wastewater Treatment object is wastewater of caprolactam production, and before process, in waste water, COD levels index is as follows:
COD (chemical oxygen demand (COD)): 5200mg/L, PH=10.5, specific conductivity=12000s.
Adopt of the present invention to above-mentioned waste water
the application method of porous graphite electrode in Industrial Wastewater Treatmentprocess, in step (2), regulate the pH value to 12 of waste water; In step (3), electrolysis time is 50 minutes, and after electrolysis, water quality PH is 7.5; In step (4), regulate the PH=12 of water; Continue again to use other art breading finally by after step (5) and (6) flocculation sediment and filtration.
Described waste water is after above electrochemical process, and after process, the sampling analysis result of clear water is as follows:
Caprolactam Industry Wastewater:
| Waste water title | Treatment process | Electrolysis time | PH | COD | Removal efficiency |
| The former water of hexanolactam | 10.5 | 5200 | |||
| After hexanolactam electrolysis | Direct Electrolysis | 50min | 7.7 | 975 | 81.2％ |
Owing to being the organic pollutant wastewater containing high density, follow-up in conjunction with Fenton process continuation process.
Embodiment three
Industrial Wastewater Treatment object is terephthalic acid and Glycol Wastewater, and before process, in waste water, COD levels index is as follows:
COD (chemical oxygen demand (COD)): 7300mg/L, PH=2.95, specific conductivity=11900s.
Adopt application method of the present invention to process to above-mentioned waste water, in step (2), regulate the pH value to 2.95 of waste water; In step (3), electrolysis time is 60 minutes, and after electrolysis, water quality PH is 3.0; In step (4), regulate the PH=11 of water; Continue again to use other art breading finally by after step (5) and (6) flocculation sediment and filtration.
Analytical results after terephthalic acid and Glycol Wastewater electrolysis is as follows:
| Waste water title | Treatment process | Electrolysis time | PH | COD | Removal efficiency |
| The former water of terephthalic acid | 2.95 | 7300 | |||
| After terephthalic acid electrolysis | Electrolysis | 60min | 3.00 | 2140 | 70.6％ |
Owing to being the organic pollutant wastewater containing high density, follow-up in conjunction with Fenton process continuation process.
Embodiment four
The nano-carbon powder that mass ratio is 5% is added in Graphite Powder 99 and binding agent, the resistance of the Graphite Electrodes made has obvious change, do not contain the resistance of the porous graphite electrode of nano-sized carbon between 20-60 ohm/10cm (length), the resistance adding the porous graphite electrode of nano-sized carbon is reduced between 5-20 ohm/10cm (length), and the porous graphite electrode therefore adding nano-carbon powder significantly can reduce the current consumption of electrolysis.
The waste water identical by embodiment three is done experiment, and the electrode of just electrolysis is the above-mentioned porous graphite electrode containing nano-sized carbon.
Adopt the described porous graphite electrode containing nano-sized carbon 5% to be processed by application method of the present invention to above-mentioned waste water, in step (2), regulate the pH value to 2.95 of waste water; In step (3), electrolysis time is 60 minutes, and after electrolysis, water quality PH is 3.0; In step (4), regulate the PH=11 of water; Continue again to use other art breading finally by after step (5) and (6) flocculation sediment and filtration.
Analytical results after terephthalic acid and Glycol Wastewater electrolysis is as follows:
| Waste water title | Treatment process | Electrolysis time | PH | COD | Removal efficiency |
| The former water of terephthalic acid | 2.95 | 7300 | |||
| After terephthalic acid electrolysis | Electrolysis | 60min | 3.00 | 1428 | 80.4％ |
Owing to being the organic pollutant wastewater containing high density, follow-up in conjunction with Fenton process continuation process.
From the result of embodiment three and embodiment four, identical waste water is being carried out in the process of electrolysis treatment, use identical processing method and parameter, but use the porous graphite electrode adding nano-sized carbon than not being significantly improved containing the result of the porous graphite electrode of nano-sized carbon.
The present invention will have the porous graphite electrode of conductive capability to be placed in pending waste water, adopt high-frequency and high-voltage impulse power supply to be energized in water and electrochemical reaction occurs, produce four kinds of effects such as oxidation, reduction, flocculation and air supporting, metallic reducing or oxidation is made by electron exchange process in electrolysis, the ion of part high-valence state is reduced at a low price or zero-valent state, make most ionic state metal be converted into the solid particulate postprecipitation of molecular state, thus remove heavy metal in water.Waste water containing a lot of organic pollutant (as oils, tensio-active agent) and various chemical industry is in the method for Industrial Wastewater Treatment of the present invention, effectively can be degraded into by the generation of hydroxyl polar radicals in electrolytic process the solid matter being easy to flocculation sediment, make trade effluent pass through adopt the electrochemical process for treating of porous graphite electrode and be purified.
Claims (6)
1. the application method of a porous graphite electrode in Industrial Wastewater Treatment, electrochemical process is adopted to process trade effluent, it is characterized in that: described method adopts porous graphite electrode as the electrode of electrolysis, this porous graphite electrode is cubes, sintered by Graphite Powder 99 and binding agent and form, its inside is provided with the some through holes forming cellular porosity.
2. the application method of porous graphite electrode according to claim 1 in Industrial Wastewater Treatment, is characterized in that: described porous graphite electrode contains nano-sized carbon.
3. the application method of porous graphite electrode according to claim 2 in Industrial Wastewater Treatment, is characterized in that: the mass ratio that described nano-sized carbon accounts for described porous graphite electrode is 5%.
4. the application method of porous graphite electrode according to claim 1 and 2 in Industrial Wastewater Treatment, is characterized in that: the concrete technology step of described method is as follows:
(1) in electrochemical cell by multiple described porous graphite electrode superposition to form electrolysis electrode, during superposition each porous graphite electrode cubes on through hole interpenetrate or intermesh;
(2) in PH equalizing tank, according to the difference of institute's metal ion and Components of Organic Pollutants in trade effluent and the difference of concentration, the pH value of trade effluent is regulated;
(3) trade effluent regulated through PH is injected electrochemical cell, adopt Industrial Wastewater Treatment power supply to carry out electrolysis to trade effluent energising;
(4) trade effluent after electrolysis enters PH equalizing tank, requires the pH value of the trade effluent after electrolysis to be adjusted to 8-12 according to the difference of various trade effluent;
(5) add flocculation agent in the trade effluent after regulating through PH, accelerate to produce and precipitate and remove throw out;
(6) supernatant water after removing throw out carries out the reprocessing of next technique after filtering or directly discharges.
5. the application method of porous graphite electrode according to claim 4 in Industrial Wastewater Treatment, is characterized in that: in described step (2), the pH value of trade effluent is adjusted to 2-12.
6. the application method of porous graphite electrode according to claim 4 in Industrial Wastewater Treatment, it is characterized in that: in described step (3), the voltage needed for electrolysis, electric current and time determine according to the composition of institute's metal ion and organic pollutant in trade effluent and concentration.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105776683A (en) * | 2016-05-11 | 2016-07-20 | 常熟林润氟硅材料有限公司 | High-frequency pulse electrochemical wastewater treatment system |
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| CN102887567A (en) * | 2012-10-11 | 2013-01-23 | 南开大学 | Method for modifying graphite felt material applied to electro-Fenton system |
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| EP0814060A2 (en) * | 1996-06-17 | 1997-12-29 | Verein für Kernverfahrenstechnik und Analytik Rossendorf e.V. | Process for increasing the pH of acidic water |
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