CN202400888U - Device for treating sewage through advanced oxidation - Google Patents
Device for treating sewage through advanced oxidation Download PDFInfo
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- CN202400888U CN202400888U CN2011204421891U CN201120442189U CN202400888U CN 202400888 U CN202400888 U CN 202400888U CN 2011204421891 U CN2011204421891 U CN 2011204421891U CN 201120442189 U CN201120442189 U CN 201120442189U CN 202400888 U CN202400888 U CN 202400888U
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Abstract
The utility model relates to a device for treating sewage through advanced oxidation. The device disclosed by the utility model comprises a barrel, an upper sealing head and a device base, wherein the lower part in the barrel is provided with a retainer plate, the lower part of the retainer plate is provided with an aeration disc, the aeration disc is communicated with an air inlet pipe, the lower part of the barrel is provided with a water inlet pipe, the upper part of the barrel is provided with a water outlet pipe, the interior of the barrel is provided with an electrolytic cathode and an electrolytic anode, the electrolytic cathode and the electrolytic anode are communicated with a direct current power supply in a circuit manner, catalyst is arranged at the periphery of the electrolytic cathode and the electrolytic anode, the upper part of the barrel is provided with a water outlet baffle, and the lower end of the water outlet baffle is lower than the water outlet pipe. The device disclosed by the utility model can be applied to treatment of brine waste of a refining system. The device disclosed by the utility model has the advantages of small volume, high treatment efficiency and lower investment and operation costs.
Description
Technical field
The utility model relates to the device that a kind of advanced oxidation is disposed of sewage, particularly the device of refinery system high-concentration and low-concentration brine waste.
Background technology
Along with high-sulfur, high-acid crude oil are processed ratio in cumulative year after year; Make oil in water emulsion, refractory organics organic pollutant, sulfide, ammonia nitrogen and inorganic salt isoconcentration in the sewage that the oil product course of processing produces constantly increase, particularly have obvious emulsification and cut water than the electric desalting draining and the higher oil product tank field of pollutant load of supersalinity.Although the ratio that these two types of discharged waste water account for the total quantity of wastewater effluent of enterprise is less; But the total amount of pollutant will account for more than 50% of gross contamination load; And because sewage character is relatively poor; Oil removal-unitary deoiling effect of flotation oil removing, the unitary biochemical stability of biochemical treatment to the sewage-farm all cause frequent impact influence, and serious threat is to the stably reaching standard discharging and the comprehensive qualified rate of enterprise's sewage.So should carry out classification processing to such waste water.For the present adoptable main method of the saliferous high density difficult for biological degradation organic waste water combination process that to be wet oxidation, advanced oxidation or catalyzed oxidation, anaerobism or acidification hydrolization etc. or these technology form with aerobic biochemical technology etc.
US6576144 proposes a kind of chemical oxidization method treatment of spent alkali and other wastewater treatment method; Oxygenants such as metal ion catalysts such as iron, copper, nickel, titanium, vanadium, molybdenum, cobalt and hydrogen peroxide, potassium permanganate, ozone, dioxide peroxide, Youxiaolin are added to respectively in waste lye and other waste water continuously; Catalytic oxidation takes place in plug flow reactor; Through controlling dosage and pH regulator to reach the processing intent that removes sulfide, ammonia, volatile phenol and other organic pollutant in waste lye and other waste water; But this method is owing to need add catalytic metal ion and oxidation medicament continuously; There are water outlet heavy metal contamination and chemical consumption problem, and high-concentration waste water is difficult to obtain treat effluent preferably.CN03133960.3 proposes a kind of heterogeneous multiple catalyzing electrolysis oxidation sewage treatment method and device, does solid adsorption material with particles such as gacs; With graphite, noble metal or plain carbon stool is electrode; With water-soluble iron, aluminium, magnesium or manganese metal-salt is catalyzer; With the air is oxidizing medium; Through applying the electrolysis voltage below the 36V; Solid adsorption material, electrode materials, support of the catalyst, liquid-phase catalysis, gaseous oxidizing agent are combined with processes such as electrolysis; Form a sewage physical-chemical-electrolytic processing apparatus, be used for biochemical preceding pre-treatment and the advanced treatment of wastewater behind the biochemistry with comprehensive subtractive process.This method can reach the purpose effect of degree of depth degradable organic pollutant, raising wastewater biochemical property through the catalysed oxidn of electrolysis generation radical and metal-salt; But owing to need the continuous supplementation metal salt catalyst; Cause the consumption of metal-salt on the one hand; Make the metal content in the water outlet increase on the other hand, be prone to form water outlet generation heavy metal contamination.
In addition; The brine waste of lower concentrations such as the acidic and alkaline waste water of the ion exchange resin regeneration of recirculated water field sewer, chemical water station discharge at present, steam boiler blowdown; Never getting into the sewage-farm handles; Along with recirculated water field make up water is used reuse water, and the raising of standard, such water can not satisfy the requirement of qualified discharge.At present to such waste water the most typical method be to adopt ultrafiltration-r-o-(" two embrane method ") or membrane bioreactor-ultrafiltration-r-o-(" three embrane methods ") combination process that the sewer of circulating water system is carried out advanced desalination to handle, the effluent reuse after the processing is made the make up water of oiler feed, chemical water station or recirculated water.The main problem that this processing mode exists at present has two: the firstth, and the organic pollutant in the water of source can not be effectively controlled, and is prone to cause ultra-filtration membrane and reverse osmosis membrane to pollute, and causes the treating processes can't long-period stable operation; It two is that COD concentration in the reverse osmosis concentrated liquid draining is higher, can not satisfy the water quality reaching standard emission request.
To sum up analyze, adopts present the whole bag of tricks to handle refinery system high density saliferous composite waste and all exist or be not suitable for or treatment effect is not enough, or be prone to problems such as generation metals ion secondary pollution.And the lower concentration brine wastes such as tail water of the recirculated water blowdown of petroleum chemical enterprise, sewage reverse osmosis desalination processing still do not have effective treatment measures up to standard.
Summary of the invention
The utility model has the higher specific conductivity and the character of difficult for biological degradation to the high and low concentration saline sewage of oil refining, proposes the reaction unit that a kind of advanced oxidation is handled.
The utility model advanced oxidation waste disposal plant comprises: the bottom is provided with grid plate in cylindrical shell, upper cover and the device pedestal, cylindrical shell; The grid plate bottom is provided with aeration plate, and aeration plate communicates with inlet pipe, and the cylindrical shell bottom is provided with water inlet pipe; Cylindrical shell top sets out water pipe; Barrel is provided with electrolysis cathode and electrolytic anode, and electrolysis cathode and electrolytic anode are communicated with circuit mode with direct supply, and catalyzer is set around electrolysis cathode and the electrolytic anode; On cylindrical shell top the water outlet baffle plate is set, water outlet baffle plate lower end height is lower than rising pipe.
In the utility model device, cylindrical shell top is fixedly connected with upper cover through flange; The cylindrical shell bottom is fixed through flange and device pedestal; Electrolytic anode and electrolysis cathode are plank frame or club shaped structure; The quantity of electrolytic anode and electrolysis cathode is provided with one group or some groups according to the scale of device; The mesh diameter of grid plate should be less than the granules of catalyst diameter that uses; In bottom of device mud discharging mouth can be set.
In the utility model device, the voltage of direct supply is 5～30V, is preferably 10～25V; Anode material is selected Ti-Zn alloy sheets, Ti-Mn alloy sheets, Ti-Ni alloy sheets or graphite cake for use, and cathode material is selected Ti-Zn alloy sheets, Ti-Mn alloy sheets, Ti-Ni alloy sheets, graphite cake or stainless steel plate for use; Fill the granules of catalyst that accounts for cylindrical shell volume 5%～30% in the cylindrical shell; Granules of catalyst is an activated carbon granule loaded metal component; Carrier particle diameter 0.5～2mm, metal component comprises one or more in cobalt, copper, iron, manganese, nickel, vanadium and the titanium, metal content is 1%～15% of a quality of activated carbon.
The utility model device in use, waste water gets into reactor drums continuously by water inlet pipe 2, the direct current that is applied between the reactor drum cathode-anode plate, voltage is 5～30V, is preferably 10～25V; Reactor drum inner anode and negative electrode are all processed tabular or bar-shaped; Select one group of positive plate and negative plate for use; Perhaps many group positive plates and negative plate alternately distribute; Anode is selected Ti-Zn alloy sheets, Ti-Mn alloy sheets, Ti-Ni alloy sheets or graphite cake for use, and negative electrode is selected Ti-Zn alloy sheets, Ti-Mn alloy sheets, Ti-Ni alloy sheets, graphite cake or stainless steel plate for use; Fill the granules of catalyst that accounts for reactor volume 5%～30% in the reactor drum; Granules of catalyst is an activated carbon granule loaded metal component; Carrier particle diameter 0.5～2mm, metal component comprises cobalt, copper, iron, manganese, nickel, vanadium or titanium, metal content is 1%～15% of a quality of activated carbon.Gaseous oxidant gets into reactor drum by inlet pipe 1 simultaneously; With traverse baffle 6 under acting in conjunction, make granules of catalyst 7 between electrode, be in fluidized state, simultaneously gaseous oxidant gets into reactor drums by inlet pipe 1 through aeration plate 7; Under the acting in conjunction of traverse baffle 11; Make granules of catalyst 8 in reactor drum, be in boiling state, carry out the advanced oxidation reaction simultaneously, the water outlet after the apparatus processes is then discharged by the water outlet 12 on device top.For guaranteeing that waste water reaches oxide treatment effect efficiently, control waste water is 1.0～7.0h in the liquid air speed of reactor drum
-1, 2.0～5.0h preferably
-1, the direct supply current control is at 0.1～10A, preferably 0.5～5A.Above-mentioned concrete operations condition can require concrete definite according to influent quality situation and effluent characteristics.
The utility model has the characteristic of high conductance based on brine waste; According to know-whies such as electrolysis, catalyzed oxidation, ozone oxidation; Electrolytic oxidation, catalyzed oxidation, ozone oxidation, liquid bed etc. are organically combined, form liquid bed advanced oxidation processing reaction device.Adopt the method processing oil refining high density saline sewage of the utility model can adopt activated sludge process further to carry out biochemical treatment, thereby can realize qualified discharge or reuse; Petroleum chemical enterprise's saliferous through after the processing of this reaction unit is high, and the sewage that pollutent is low can satisfy new strict emission standard controlling index requirement.
This device can be used for the pre-treatment of the high organic concentration brine waste of petroleum chemical enterprise, but further biochemical treatment qualified discharge also can be used for the processing of the low organic concentration brine waste of refinery system.This equipment has that volume is little, processing efficiency is high, the secondary pollution of treat effluent non-metallic ion, investment and the lower advantage of working cost.
Description of drawings
Fig. 1 is the structural representation of a kind of advanced oxidation reaction unit of the utility model;
Fig. 2 is a grid plate structural representation among Fig. 1.
1-inlet pipe among the figure; The 2-water inlet pipe; The 3-grid plate; 4-device pedestal; The 5-mud discharging mouth; The 6-lower flange; The 7-aeration plate; The 8-granules of catalyst; 9-battery lead plate or rod; Optional battery lead plate of 10-or rod; 11-water outlet baffle plate; The 12-water outlet; The 13-upper flange; The 14-upper cover; The 15-D.C. regulated power supply.
Embodiment
Describe below in conjunction with the concrete technological process of accompanying drawing the utility model method.
Waste water gets in the reactor drum by water inlet pipe 2 continuously; Mixing boiling with composite waste and granules of catalyst 8 flows; Start D.C. regulated power supply 15 simultaneously, make between anodic-cathodic plate or rod 9 and the granules of catalyst 8 and produce current field, under the effect of electrolysis electrode, granules of catalyst and oxidation by ozone gas agent; The reaction of generation advanced oxidation, the water outlet that goes out water reactor top 12 dischargers after the apparatus processes.
In the advanced oxidation reaction unit that the utility model proposed, positive plate and negative plate are fixing by the upper flange 13 on electrolysis reactor top.Catalyst filling particle 8 in the reactor drum is selected the conventional gac of the particulate state with certain electroconductibility for use; Metal component comprises cobalt, copper, iron, manganese, nickel, vanadium or titanium, and metal content is 1%～15% of a quality of activated carbon.Its preparation method can adopt the method for the description of US6797184 to prepare.
Adopt the advanced oxidation reaction unit and the treatment process of the utility model that petroleum chemical enterprise's brine waste is handled; Can make that difficult for biological degradation property organic constituent obtains the removal more than 70% in the waste water; But the further biochemical treatment qualified discharge of high organic concentration brine waste, low directly qualified discharge or reuse of organic concentration brine waste.
Further specify the utility model method and effect through embodiment below.
Embodiment 1
The treatment unit of employing the utility model is cut two kinds of high density composite wastes of water to domestic certain refinery electric desalting apparatus draining, oil product tank field and is carried out processing up to standard.Composite waste COD 2800 mg/L, sulfide 460 mg/L, petroleum-type 120 mg/L, ammonia nitrogen 100 mg/L.Adopt the utility model catalytic and oxidative electrolysis technology-SBR combination process to handle, the advanced oxidation reactor drum is the cell body that pmma material is processed, useful volume 10L.Respectively by establishing 4 Ti-Mn alloy sheets, alternately distribute, and insert respectively on the negative pole and positive pole of D.C. regulated power supply in the middle of the cell body.The cell body bottom opening is laid a water-in of intaking continuously in order to the micro-hole aerator and of oxygenation, and supplies ozone with ozonizer; The cell body side wall upper part is laid water outlet, in order to continuous drainage.Fill the activated carbon granule of a kind of year active copper metal in the cell body, loadings 400g (500mL).Wherein gac adopts 10～16 purpose active fruit shell carbons, and according to the method for US6797184 description reactive metal copper is written on the gac, and metallic copper content is 5% of quality of activated carbon.
The sbr reactor device is that useful volume is that the synthetic glass of 12L is processed, and adopts and stirs and the micro-hole aerator oxygenic aeration, and control the entering of waste water and air with SV, programmable logic controller (PLC) sequence control system.The waste water flow velocity 3L/h, the reactor drum two ends that get into the advanced oxidation reactor drum apply voltage 15V, electric current 3.5A, the ozone amount of blasting 400mL/min, and temperature is 30 ℃.
Catalytic and oxidative electrolysis technology reactor drum effluent quality is: COD 700 mg/L, sulfide 2.3 mg/L, petroleum-type 10mg/L, ammonia nitrogen 78mg/L.The water outlet of advanced oxidation reactor drum is handled by being pumped into the sbr reactor device at medial launder, the major control condition be 3 the cycle/day, cycle flooding time 4h, cycle intake flow velocity 4L/h, cycle air blast flow velocity 200 mL/min, settling time in cycle 0.5h.Main waste water quality after the advanced oxidation-SBR combination process of the utility model is handled is: COD 70mg/L, sulfide 0.4 mg/L, petroleum-type 3 mg/L, ammonia nitrogen 10 mg/L, satisfy the requirement of direct qualified discharge.
Embodiment 2
Adopt the treatment unit of the utility model that certain refinery circulating water system (having implemented the make up water that the oil refining sewerage fully recovering is made circulating water system) sewer is handled.Principal pollutant COD 140 mg/L in the waste water, BOD
530 mg/L, total solid 2600 mg/L, petroleum-type of dissolving<1mgL, NH
3-N<5mgL.
Advanced oxidation reaction unit and the treatment process that adopts the utility model is to the above-mentioned waste water chamber Processing Test that experimentizes.The advanced oxidation reactor drum is with embodiment 1.Main technique operational conditions: flooding quantity 3L/h; Lift gas adopts ozone, air input 24L/h.The test treatment effect: after the method processing through the utility model, the COD in the circulating water system sewer is reduced to 40mg/L, BOD
5Be reduced to and do not detect, other pollution components does not have to change basically.
Claims (9)
1. device that advanced oxidation is disposed of sewage is characterized in that comprising: the bottom is provided with grid plate in cylindrical shell, upper cover and the device pedestal, cylindrical shell; The grid plate bottom is provided with aeration plate, and aeration plate communicates with inlet pipe, and the cylindrical shell bottom is provided with water inlet pipe; Cylindrical shell top sets out water pipe; Barrel is provided with electrolysis cathode and electrolytic anode, and electrolysis cathode and electrolytic anode are communicated with circuit mode with direct supply, and catalyzer is set around electrolysis cathode and the electrolytic anode; On cylindrical shell top the water outlet baffle plate is set, water outlet baffle plate lower end height is lower than rising pipe.
2. according to the described device of claim 1, it is characterized in that: cylindrical shell top is fixedly connected with upper cover through flange; The cylindrical shell bottom is fixed through flange and device pedestal.
3. according to the described device of claim 1, it is characterized in that: electrolytic anode and electrolysis cathode are plank frame or club shaped structure; Electrolytic anode and electrolysis cathode are provided with one group or some groups.
4. according to the described device of claim 1, it is held to levy and is: the mesh diameter of grid plate is less than the granules of catalyst diameter that uses.
5. according to the described device of claim 1, it is characterized in that: mud discharging mouth is set in bottom of device.
6. according to the described device of claim 1, it is characterized in that: the voltage of direct supply is 5～30V.
7. according to claim 1,3 or 6 described devices; It is characterized in that: the anode material of electrolysis electrode is selected Ti-Zn alloy sheets, Ti-Mn alloy sheets, Ti-Ni alloy sheets or graphite cake for use, and cathode material is selected Ti-Zn alloy sheets, Ti-Mn alloy sheets, Ti-Ni alloy sheets, graphite cake or stainless steel plate for use.
8. according to the described device of claim 1, it is characterized in that: fill the catalyzer that accounts for device cylindrical shell volume 5%～30% in the cylindrical shell.
9. according to claim 1 or 6 described devices, it is characterized in that: the direct supply current control is at 0.1～10A.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011204421891U CN202400888U (en) | 2011-11-10 | 2011-11-10 | Device for treating sewage through advanced oxidation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011204421891U CN202400888U (en) | 2011-11-10 | 2011-11-10 | Device for treating sewage through advanced oxidation |
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| Publication Number | Publication Date |
|---|---|
| CN202400888U true CN202400888U (en) | 2012-08-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011204421891U Expired - Lifetime CN202400888U (en) | 2011-11-10 | 2011-11-10 | Device for treating sewage through advanced oxidation |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104326531A (en) * | 2014-11-24 | 2015-02-04 | 桑德集团有限公司 | Ozone, electrochemistry and oxidation combined water treatment reactor |
| CN104445529A (en) * | 2014-11-18 | 2015-03-25 | 北京师范大学 | Up-flow electro-catalytic reactor |
| CN105523613A (en) * | 2015-12-14 | 2016-04-27 | 江苏师范大学 | Filled-type electrocatalytic oxidation reactor based on electromagnetic induction principle |
-
2011
- 2011-11-10 CN CN2011204421891U patent/CN202400888U/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445529A (en) * | 2014-11-18 | 2015-03-25 | 北京师范大学 | Up-flow electro-catalytic reactor |
| CN104326531A (en) * | 2014-11-24 | 2015-02-04 | 桑德集团有限公司 | Ozone, electrochemistry and oxidation combined water treatment reactor |
| CN105523613A (en) * | 2015-12-14 | 2016-04-27 | 江苏师范大学 | Filled-type electrocatalytic oxidation reactor based on electromagnetic induction principle |
| CN105523613B (en) * | 2015-12-14 | 2018-05-18 | 江苏师范大学 | A kind of filled type electrocatalysis oxidation reaction device based on electromagnetic induction principle |
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| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20120829 |