CN102126778A - Groove-type device and method for treating organic wastewater by multiphase electro-catalytic oxidation - Google Patents

Groove-type device and method for treating organic wastewater by multiphase electro-catalytic oxidation Download PDF

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Publication number
CN102126778A
CN102126778A CN 201110028360 CN201110028360A CN102126778A CN 102126778 A CN102126778 A CN 102126778A CN 201110028360 CN201110028360 CN 201110028360 CN 201110028360 A CN201110028360 A CN 201110028360A CN 102126778 A CN102126778 A CN 102126778A
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China
Prior art keywords
waste water
catalytic oxidation
groove
oxidation
organic waste
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Chinese (zh)
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梅荣武
韦彦斐
沈浙萍
李欲如
张钢
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Zhejiang Environmental Science Research and Design Institute
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Zhejiang Environmental Science Research and Design Institute
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Abstract

The invention discloses a groove-type device and a method for treating organic wastewater by multiphase electro-catalytic oxidation. The device comprises an electro-catalytic oxidation tank, an electrode plate bracket, a cylindrical positive electrode, a board-shaped negative electrode, an intermediate medium, a catalyst, a water inlet, a gas inlet, a water outlet, a tank body support, an internal medium support and an overflow tank. The method comprises the following steps of: adding acidic organic wastewater into the multiphase electro-catalytic oxidation tank, and adding an oxidizing agent at the same time; performing electro-catalytic oxidation reaction in the electro-catalytic oxidation tank, wherein the electrode is graphite-loaded titanium dioxide, the catalyst is acid-proof magnet powder and goethite powder, the intermediate medium is convex-concave rod soil and tourmaline and the oxidizing agent is hydrogen peroxide, air, chlorine dioxide and potassium permanganate; adding alkali liquid or lime water into the wastewater obtained after the reaction to adjust the pH value of the wastewater to be 7; adding the wastewater into a sedimentation basin for sedimentation; and adding the wastewater obtained after the sedimentation into a biochemical treatment system for treatment. The device and the method have the advantages of high treatment efficiency, small floor space, low operation cost and the like.

Description

Organic waste water slot-type device and method thereof are handled in a kind of polyphase electrocatalytic oxidation
Technical field
The present invention relates to high concentrated organic wastewater treatment unit and method thereof, relating in particular to mainly is the method that adopts polyphase electrocatalytic oxidation technical finesse high concentrated organic wastewater.Belong to technical field of sewage.
Background technology
Along with the fast development of industries such as China's chemical industry, medicine, dyestuff, the economic strength of China is progressively improved; Simultaneously, the parallel therewith waste water environmental pollution that is in the production process to be discharged also increasingly sharpens, human beings'health is formed serious threat.The waste water of industries such as chemical industry, medicine, dyestuff is big because of complicated component, organic content height, saliferous height, colourity and toxicity, handle the technical difficulty greatly that still all exists economically of this type of waste water, burning method that general employing energy consumption is higher or big multiple dilution back biochemical treatment after simple apparent processing, it is high that these class methods are handled often investment, floor space is big, the working cost height, the user is difficult to bear.
High concentrated organic wastewater oxide treatment technology is research focus, the technological difficulties in current environmental protection field.Polyphase electrocatalytic oxidation method is to utilize the effective catalyst of up-to-date exploitation, the energising back is by the effect of oxygenant, the waste water that complicated component, organic content height, saliferous height, colourity and toxicity is big carries out destructive oxidation under relatively mild condition, this is a kind of a kind of oxidation technology that the state-of-the-art technology of chemical field is combined with corresponding effective catalyst, has represented the main trend of external this type of waste water control.Advantages such as this technology has the processing efficiency height, suitability is wide, processing cost is lower, convenient operation and management have broad application prospects.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of polyphase electrocatalytic oxidation to handle organic waste water slot-type device and method thereof.
The polyphase electrocatalytic oxidation is handled the organic waste water slot-type device and comprised: the organic waste water slot-type device is handled in a kind of polyphase electrocatalytic oxidation, it is characterized in that comprising catalytic oxidation groove, battery lead plate support, cylindricality anode, plate shape negative electrode, intermediate medium, catalyzer, water-in, inlet mouth, water outlet, cell body support, interior dielectric support and overflow groove; Catalytic oxidation groove lower end is provided with cell body and supports, catalytic oxidation groove upper end is provided with overflow groove and battery lead plate support, battery lead plate support below is provided with cylindricality anode and plate shape negative electrode, catalytic oxidation groove bottom is provided with interior dielectric support, interior dielectric support is provided with intermediate medium, catalyzer, interior dielectric support below is provided with inlet mouth, and the catalytic oxidation trench bottom is provided with water-in, and overflow groove is provided with water outlet.
Intermediate medium, the intermediate medium in the catalyzer that the organic waste water slot-type device is handled in described polyphase electrocatalytic oxidation are: attapulgite and tourmalinite.
Intermediate medium, the catalyzer in the catalyzer that the organic waste water slot-type device is handled in described polyphase electrocatalytic oxidation are: acid proof magnetic iron powder ferric oxide and pyrrhosiderite powder.
Described polyphase electrocatalytic oxidation is handled the organic waste water slot-type device and is adopted steel, and glass inner-lining steel fiber and Resins, epoxy are anticorrosion.
The organic waste water method is handled in the polyphase electrocatalytic oxidation of described device: organic waste water is regulated pH earlier with sulfuric acid or sodium hydroxide makes it be acid, organic waste water is entered in the polyphase electrocatalytic oxidation groove by polyphase electrocatalytic oxidation trench bottom then, simultaneously, add oxygenant in the waste water, wherein oxygenant is hydrogen peroxide, air, dioxide peroxide and potassium permanganate, in the catalytic oxidation groove, carry out electrocatalysis oxidation reaction, the catalytic oxidation time is 2~8h, interelectrode volts DS is 5~15V, and current density is 2~20mA/cm 2, reacted wastewater adds liquid caustic soda or liming is regulated pH value to 7, enters the settling tank precipitation again, and the waste water of post precipitation enters biochemical treatment system and handles.
Described organic waste water by the water intake mode that polyphase electrocatalytic oxidation trench bottom enters polyphase electrocatalytic oxidation groove is: Inlet and outlet water continuously or intermittently.
The beneficial effect that the present invention compared with prior art has:
(1) realized polyphase electrocatalytic oxidation under acidic conditions.
(2) used the acid proof catalyzer.
(3) electrode materials has been selected semiconductor medium for use, has improved processing efficiency.
(4) treatment scheme is simple, and is easy and simple to handle, can realize automatization control.
Description of drawings
Fig. 1 is the structure iron of electrocatalysis oxidation apparatus of the present invention.
Among the figure, catalytic oxidation groove 1, battery lead plate support 2, cylindricality anode 3, plate shape negative electrode 4, intermediate medium, catalyzer 5, water-in 6, inlet mouth 7, water outlet 8, cell body support 9, interior dielectric support 10 and overflow groove 11.
Embodiment
The polyphase electrocatalytic oxidation is handled the organic waste water slot-type device and is comprised: catalytic oxidation groove 1, battery lead plate support 2, cylindricality anode 3, plate shape negative electrode 4, intermediate medium, catalyzer 5, water-in 6, inlet mouth 7, water outlet 8, cell body support 9, interior dielectric support 10 and overflow groove 11; Catalytic oxidation groove 1 lower end is provided with cell body and supports 9, catalytic oxidation groove 1 upper end is provided with overflow groove 11 and battery lead plate support 2, battery lead plate support 2 belows are provided with cylindricality anode 3 and plate shape negative electrode 4, catalytic oxidation groove 1 bottom is provided with interior dielectric support 10, interior dielectric support 10 is provided with intermediate medium, catalyzer 5, interior dielectric support 10 belows are provided with inlet mouth 7, and catalytic oxidation groove 1 bottom is provided with water-in 6, and overflow groove 11 is provided with water outlet 8.
The intermediate medium of organic waste water slot-type device is handled in described polyphase electrocatalytic oxidation, the intermediate medium in the catalyzer 5 is: attapulgite and tourmalinite.
The intermediate medium of organic waste water slot-type device is handled in described polyphase electrocatalytic oxidation, the catalyzer in the catalyzer 5 is: acid proof magnetic iron powder Z 250 and pyrrhosiderite powder.
Described polyphase electrocatalytic oxidation is handled the organic waste water slot-type device and is adopted steel, and glass inner-lining steel fiber and Resins, epoxy are anticorrosion.
The organic waste water method is handled in the polyphase electrocatalytic oxidation of described device: organic waste water is regulated pH earlier with sulfuric acid or sodium hydroxide makes it be acid, organic waste water is entered in the polyphase electrocatalytic oxidation groove by polyphase electrocatalytic oxidation trench bottom then, simultaneously, add oxygenant in the waste water, wherein oxygenant is hydrogen peroxide, air, dioxide peroxide and potassium permanganate, in the catalytic oxidation groove, carry out electrocatalysis oxidation reaction, the catalytic oxidation time is 2~8h, interelectrode volts DS is 5~15V, and current density is 2~20mA/cm 2, reacted wastewater adds liquid caustic soda or liming is regulated pH value to 7, enters the settling tank precipitation again, and the waste water of post precipitation enters biochemical treatment system and handles.
Described organic waste water by the water intake mode that polyphase electrocatalytic oxidation trench bottom enters polyphase electrocatalytic oxidation groove is: Inlet and outlet water continuously or intermittently.
The organic waste water concrete operation method is handled in the polyphase electrocatalytic oxidation of described device: with the pH value of sulfuric acid or sodium hydroxide adjusting organic waste water, generally be controlled at 1~3 earlier.The waste water of adjusting the pH value squeezed in the polyphase electrocatalytic oxidation groove by corrosion-resistant sump pump carry out catalyzed oxidation, oxidization time is 2~8h, and interelectrode volts DS is 5~15V, and current density is 2~20mA/cm 2, can adjust according to different influent qualities and degree of treatment.Electrode is a graphite loaded titanium dioxide; Catalyzer is acid proof magnetic iron powder Z 250 and pyrrhosiderite powder.Intermediate medium is attapulgite and tourmalinite; The ratio of adding is: 1:1~5:1, dosage are 20~60% of cubic capacity; Oxygenant is hydrogen peroxide, air, dioxide peroxide and potassium permanganate.Under the effect of extra electric field, carry out the polyphase electrocatalytic oxidation: utilize intermediate medium with the catalysis of helping and adsorption function such as attapulgite and tourmalinite that organic pollutant enrichment is arrived dielectric surface; Because the adsorptive power of various adsorption mediums is different with adsorption range, can adsorb each pollutant.Pollutent is enriched to solid phase surface continuously from water, under normal temperature, condition of normal pressure, can under the multiple synergy of oxygenant, catalyzer, electric field, be decomposed fast continuously, changed the structure of feature pollutent in the waste water such as phenyl ring, heterocycle etc., make larger molecular organics be converted into small molecules or carbonic acid gas and water, handle organic purpose thereby reach continuous high-efficient, also can improve the biodegradability of waste water.Polyphase electrocatalytic oxidation reacted wastewater pH value can bring up to 4~6, adds liquid caustic soda or liming and regulates pH value to 7~8, enters the settling tank precipitation again, and the waste water of post precipitation enters biochemical treatment system and handles.
Catalytic oxidation mechanism: have the active substance of strong oxidizing property to exist in the electrocatalysis system, these active substances comprise H 2O 2, O 3, HO -, HO 2 -, O 2 -And solvated electron e sDeng, if in the solution Cl is arranged -Exist, also have Cl 2, HClO -And ClO _Exist in oxygenant.The existence of these strong oxidizing property materials can improve the ability of degradation of organic substances greatly.Table 1 has been listed part strong oxidizing property standard of physical reducing electrode electromotive force.
Table 1 strong oxidizing property standard of physical reducing electrode electromotive force table
The strong oxidizer kind Standard potential/V ? The strong oxidizer kind Standard potential/V
HO . 2.80 ? H 2O 2 1.78
O 2 - 2.42 ? HO 2 - 1.70
O 3 2.07 ? Cl - 1.36
As can be seen from the above table, they all have quite high reduction potential, can the most of organism of oxidation.
In the electrocatalysis system, by the O of electrolysis generation 2Or the extraneous O that provides 2, reduction can produce H on negative electrode 2O 2
Under the acidic conditions: O 2+ 2H ++ 2e -H 2O 2
Under the alkaline condition: O 2+ H 2O+2e -HO 2 -+ OH -
HO 2 -+H 2O+2e -????H 2O 2+OH -
And the HO in the system , can under the effect of metal catalyst, produce:
Under the acidic conditions: M Red+ H ++ H 2O 2M Ox+ HO .+ H 2O
Under the alkaline condition: M Red+ H 2O 2Mox+HO .+ OH -
At HO -Effect under, quick oxidizing reaction and radical chain reaction take place in organism, thereby are degraded rapidly.
The Ti0 of mineral carbon load 2Be semiconductor material.The energy band structure of semiconductor particle generally is made of valence band of filling up electronics and empty high energy conduction band, has the forbidden band between valence band and the conduction band, after energising, and outside under the effect of electric field, because energy is greater than energy gap, the electronics (e on the semi-conductor valence band One) being excited transits to conduction band formation high-energy electron (e One), on valence band, produce hole (h +), and under electric field action, move to particle surface respectively.High-energy electron (e One) easily caught by oxidizing substances such as oxygen in water, and the hole has very strong oxidation capacity because of having the extremely strong ability of obtaining electronics, can be with the organism or the OH of its surface adsorption -And H 20 molecular oxygen changes into the OH free radical, and the OH free radical does not almost have selectively with oxidation operation in the water.
Utilize lotus roots such as chemical catalytic oxidation, catalytic oxidation, chemical oxidation, electrocoagulation to close the technical finesse high concentrated organic wastewater on the task,, improve the biodegradability of waste water, propose mark, qualified discharge and middle water reuse for waste water and create conditions to reduce the toxicity of waste water.
Embodiment 1: organic silicon wastewater is handled
Organic silicon wastewater is regulated pH earlier with sulfuric acid makes it be acid, organic silicon wastewater is entered in the polyphase electrocatalytic oxidation groove by polyphase electrocatalytic oxidation trench bottom then, simultaneously, add oxygenant in the waste water, wherein oxygenant is a hydrogen peroxide, carries out electrocatalysis oxidation reaction in the catalytic oxidation groove, and the catalytic oxidation time is 8h, interelectrode volts DS is 15V, and current density is 20mA/cm 2, reacted wastewater adds liquid caustic soda and regulates pH value to 7, enters the settling tank precipitation again, and the waste water of post precipitation enters biochemical treatment system and handles.
Organosilane monomer production institute effluent organic concentration height, the saltiness height, biodegradability is poor.Concrete water quality parameter sees Table 1-1.
Table 1-1 organic silicon wastewater water quality list position: mg/l
Organic silicon wastewater electricity consumption catalysed oxidation processes is handled, and long run test 8h gets sample one time every 2h, measures COD respectively Cr, Cl -Test-results sees Table the former water COD of 1-2( CrBe 2850mg/l).
Table 1-2 catalytic oxidation test-results
Batch 2h 4h 6h 8h
COD cr(mg/L) 2.48×10 3 1.12×10 3 1.25×10 3 1.27×10 3
Clearance (%) 13.0 70.9 56.1 55.4
Cl -(mg/L) 2.12×10 4 1.82×10 4 1.73×10 4 1.83×10 4
Embodiment 2: the organophosphorus wastewater treatment
Glyphosate production wastewater is regulated pH earlier with sulfuric acid makes it be acid, glyphosate production wastewater is entered in the polyphase electrocatalytic oxidation groove by polyphase electrocatalytic oxidation trench bottom then, simultaneously, add oxygenant in the waste water, wherein oxygenant is a hydrogen peroxide, carries out electrocatalysis oxidation reaction in the catalytic oxidation groove, and the catalytic oxidation time is 2h, interelectrode volts DS is 5V, and current density is 2mA/cm 2, reacted wastewater adds liming and regulates pH value to 7, enters the settling tank precipitation again, and the waste water of post precipitation enters biochemical treatment system and handles.
Glyphosate production wastewater organic concentration height, the saltiness height, organophosphorus content height, intractability is big.This production technique wastewater pH: 1~2, COD Cr: 20000~30000mg/l; Total phosphorus (based on organophosphorus)〉1000mg/l.
Glyphosate production wastewater electricity consumption catalysed oxidation processes is handled, and long run test 2h measures COD respectively Cr, TP.Record post precipitation supernatant C OD CrClearance is greater than 40%, and total tp removal rate is greater than 75%.

Claims (6)

1. the organic waste water slot-type device is handled in a polyphase electrocatalytic oxidation, it is characterized in that comprising that catalytic oxidation groove (1), battery lead plate support (2), cylindricality anode (3), plate shape negative electrode (4), intermediate medium, catalyzer (5), water-in (6), inlet mouth (7), water outlet (8), cell body support (9), interior dielectric support (10) and overflow groove (11); Catalytic oxidation groove (1) lower end is provided with cell body and supports (9), catalytic oxidation groove (1) upper end is provided with overflow groove (11) and battery lead plate support (2), battery lead plate support (2) below is provided with cylindricality anode (3) and plate shape negative electrode (4), catalytic oxidation groove (1) bottom is provided with interior dielectric support (10), interior dielectric support (10) is provided with intermediate medium, catalyzer (5), interior dielectric support (10) below is provided with inlet mouth (7), catalytic oxidation groove (1) bottom is provided with water-in (6), and overflow groove (11) is provided with water outlet (8).
2. the organic waste water slot-type device is handled in a kind of polyphase electrocatalytic oxidation according to claim 1, it is characterized in that the intermediate medium in described intermediate medium, the catalyzer (5) is: attapulgite and tourmalinite.
3. the organic waste water slot-type device is handled in a kind of polyphase electrocatalytic oxidation according to claim 1, it is characterized in that the catalyzer in described intermediate medium, the catalyzer (5) is: acid proof magnetic iron powder Z 250 and pyrrhosiderite powder.
4. the organic waste water slot-type device is handled in a kind of polyphase electrocatalytic oxidation according to claim 1, it is characterized in that described catalytic oxidation groove (1) adopts steel, and glass inner-lining steel fiber and Resins, epoxy are anticorrosion.
5. the organic waste water method is handled in the use polyphase electrocatalytic oxidation of installing according to claim 1, it is characterized in that organic waste water makes it be acid with sulfuric acid or the adjusting pH of sodium hydroxide elder generation, organic waste water is entered in the polyphase electrocatalytic oxidation groove by polyphase electrocatalytic oxidation trench bottom then, simultaneously, add oxygenant in the waste water, wherein oxygenant is a hydrogen peroxide, air, dioxide peroxide and potassium permanganate, in the catalytic oxidation groove, carry out electrocatalysis oxidation reaction, the catalytic oxidation time is 2~8h, interelectrode volts DS is 5~15V, and current density is 2~20mA/cm 2, reacted wastewater adds liquid caustic soda or liming is regulated pH value to 7, enters the settling tank precipitation again, and the waste water of post precipitation enters biochemical treatment system and handles.
6. the organic waste water method is handled in a kind of polyphase electrocatalytic oxidation according to claim 5, it is characterized in that described organic waste water by the water intake mode that polyphase electrocatalytic oxidation trench bottom enters polyphase electrocatalytic oxidation groove is: Inlet and outlet water continuously or intermittently.
CN 201110028360 2011-01-26 2011-01-26 Groove-type device and method for treating organic wastewater by multiphase electro-catalytic oxidation Pending CN102126778A (en)

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CN103755099A (en) * 2014-01-20 2014-04-30 厦门绿动力环境治理工程有限公司 Multidimensional poleless electro-oxidation wastewater treatment method
CN105084648A (en) * 2015-07-21 2015-11-25 昆山美淼环保科技有限公司 Treatment method for hardly biodegraded sewage
CN106365258A (en) * 2016-09-06 2017-02-01 深圳市君想环境科技有限公司 Three-dimensional electrode electrocatalytic oxidization device for high-salt-content high-COD (chemical oxygen demand) wastewater

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CN101863533A (en) * 2010-06-25 2010-10-20 合肥工业大学 Internal recycle multi-dimensional electro-catalytic wastewater treating equipment

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CN1163419C (en) * 2000-08-23 2004-08-25 中国科学院大连化学物理研究所 Process for treating industrial waste water of chemical fertilizer plant by electric multiple phasec catalytic technology
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CN2926204Y (en) * 2006-06-28 2007-07-25 珠海九通环境工程有限公司 Sewage treating trough with electrocatalytic oxidation functions
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103755099A (en) * 2014-01-20 2014-04-30 厦门绿动力环境治理工程有限公司 Multidimensional poleless electro-oxidation wastewater treatment method
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CN105084648A (en) * 2015-07-21 2015-11-25 昆山美淼环保科技有限公司 Treatment method for hardly biodegraded sewage
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Application publication date: 20110720