CN105036423A - Electrolytic treatment system of ship domestic sewage - Google Patents
Electrolytic treatment system of ship domestic sewage Download PDFInfo
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- CN105036423A CN105036423A CN201510356596.3A CN201510356596A CN105036423A CN 105036423 A CN105036423 A CN 105036423A CN 201510356596 A CN201510356596 A CN 201510356596A CN 105036423 A CN105036423 A CN 105036423A
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Abstract
An electrolytic treatment system of ship domestic sewage adopts the structure that the outlet of a sewage collection tank is connected with the inlet of an electric flocculation unit through a crushing pump, the outlet of a first seawater pump is also connected with the inlet of the electric flocculation unit, and the water outlet of the electric flocculation unit is connected with the inlet of an intermediate collection tank; the water outlet of the intermediate collection tank is sequentially connected with the inlet of an electrolysis unit and a chlorine elimination unit in series through a second seawater pump, and sewage subjected to chlorine elimination of the chlorine elimination unit is discharged by a drainage pump; a sewage outlet is formed in the lower end of each of the sewage collection tank, the electric flocculation unit, the intermediate collection tank and the chlorine elimination unit; a hydrogen discharge outlet and an air inlet are formed in the top of the chlorine elimination unit, and the air inlet is connected with an explosion-proof blower. The electrolytic treatment system has the advantages that as an oxide anode of novel manufacture process and composition is adopted, the current density of the electrolysis unit is reduced, the sewage residence time is shortened, meanwhile, the treatment parameters of other treatment units in the treatment system are correspondingly reduced, accordingly, the system size can be reduced to a certain extent, and the system energy consumption is lowered.
Description
Technical field
The present invention relates to a kind of electrolytic process Sewage from Ships treatment system, belong to ocean environment engineering field.
Background technology
Along with developing on an unprecedented scale of shipping-trade and ocean exploitation, the pollution of ocean environment is also more and more serious, and the mankind are to the protection of ocean environment also pay attention to day by day.The Sewage from Ships pollution problem brought owing to transporting by sea also causes the concern of people gradually.Boats and ships, as the vehicles in shipping, are a kind of mobile source of pollution, and the discharge of Sewage from Ships, on the impact in ocean and inland river, can not be ignored along with the increase of ships quantity.
In order to strictly control the discharge of Sewage from Ships, International Maritime Organizaton (IMO) formulated a series of relevant criterion and directive/guide from 1976 to 2012, and wherein up-to-date IMO resolution (MEPC.227 (64)) is about to enforcement in 1 day January in 2016.The concrete IMO emission request that it is provided by resolution that is in Table-1.Some existing Technology of Ship Domestic Sewage Treatment can not meet the up-to-date Sewage from Ships cleanup standard of IMO, therefore, must improve or develop new treatment technology to existing treatment technology and device.
Table-1.IMO Sewage from Ships puts requirement
Technology of Ship Domestic Sewage Treatment main is both at home and abroad biochemical process (activated sludge process, MBR method) and electrochemical process at present.Biochemical process is under certain condition, utilizes microorganism to decomposition digestion organic in sanitary sewage, generates carbonic acid gas and the water of environmental sound, thus reaches the object to sewage purification; Electrochemical method mainly utilizes electrochemical method to carry out physical removal or direct oxidation to the organism in sewage, reduces COD and BOD in water
5value, produces oxygenant simultaneously, kills intestinal bacteria in water.In addition, also need to process chlorine residue in water, make it reach emission standard.
Although biochemical process treatment technology and system number of applications more, exist treatment unit volume large, cannot process buck, water resistant power load variations poor, need special messenger to be responsible for safeguarding the shortcomings such as culturing bacterium.Electrochemical process mainly adopts electrolysis tech to process sewage, this technical finesse effect stability, and level of automation is high, but this technology still needs to improve electrolysis sewage efficiency further, extends electrode life, reduces system energy consumption, increases system stability further.
Oxide anode is the core component of electrolytic process process sanitary sewage.High catalytic performance and stable electrode materials are core and the research emphasis for the treatment of ship domestic sewage through electrolytic process.Ti base precious metal oxide compound has excellent electro catalytic activity, is widely used and research.Particularly nineteen sixty-five Dutch successfully develops Ti base RuO
2since coated anode, the extensive work of anode research just launches round metal oxide.
For the treatment of the oxide anode material of sanitary sewage, generally should possess following requirement: there is good electroconductibility; Life-span is long, and antianode reaction has good electrocatalysis characteristic.At present, a fatal defects of oxide anode is that work-ing life is short, the major cause of electrode inactivation is that Titanium base is oxidized, Titanium base Surface Creation one deck passive film, or active substance comes off or dissolved.Numerous investigator is in order to address this problem in recent years, proposes a lot of scheme.Wherein permitted vertical female people such as grade and described a kind of method for preprocessing metal oxide anode substrate, the oxide anode of preparation is made to have good stability by processing matrix, but pre-treating technology length consuming time in this patent, energy consumption is high, as long in oxalic acid etching time, the problems such as blasting craft is not good.The Sn such as Shi Yanhua, the oxide compound of Sb is as middle layer, the bonding force of enhanced activity layer and matrix, and delay passivation (EffectofSbOx+SnO2IntermediateLayeronthePropertiesofTi-ba sedMnO2Anode [J] .ActaPhys.Chim.Sin. of oxygen to matrix, 2007, 23 (10): 1553-1559.), but the content increasing middle layer can reduce oxygen evolution potential, disadvantageous to the application of titanium base oxide anode, especially in process sanitary sewage process, such as oxygen evolution potential is low is unfavorable for that organism is oxidized anodically and is beneficial to precipitated oxygen, thus reduce current efficiency.
Summary of the invention
The invention provides a kind of electrolytic process Sewage from Ships treatment system, short and the further problem improved of electrolytic efficiency needs with the life-span solving the oxide anode existence in current electrolysis method Sewage from Ships treatment system, finally makes the sewage index after process meet IMOMEPC.227 (64) resolution requirement.
Technical scheme of the present invention is: a kind of electrolytic process Sewage from Ships treatment system, it is characterized in that, comprise electric flocculation unit, electrolysis cells, disappear chlorine unit and associated vessel, pump, valve, pipeline, the outlet of sewage collecting tank is connected by the entrance of macerator pump with electric flocculation unit, first seawater pump outlet is also connected with the entrance of electric flocculation unit, and the water out of electric flocculation unit is connected with the entrance of intermediate collection tank; The water outlet of intermediate collection tank is connected with the chlorine units in series that disappears with the entrance of electrolysis cells successively through the second sea-water pump, and the sewage after the chlorine unit that disappears disappears chlorine is discharged by drainage pump; Sewage draining exit is equipped with in the lower end of sewage collecting tank, electric flocculation unit, intermediate collection tank, the chlorine unit that disappears; Be provided with hydrogen discharge mouth and gas inlet on the top of the chlorine unit that disappears, gas inlet is connected with explosion-proof fan.
Described electrolysis cells comprises electrolyzer, oxide anode and negative electrode, arranges oxide anode and negative electrode in electrolyzer; This oxide anode comprises the activated coating on Titanium base and surface thereof, and described activated coating is made up of Graphene, Au, ZrO2 and SnO2, and the molar fraction of each composition is respectively Graphene:5 ~ 20%, Au:1 ~ 3%, Zr:10 ~ 30%, Sn:55 ~ 85%, carries painting amount>=5g/m
2.
The preparation method of described oxide anode comprises the following steps:
(1) sandblasting: sandblasting is carried out to increase surfaceness to Titanium base;
(2) oil removing: the greasy dirt of the titanium-based surface after removing sandblasting;
(3) etch: the Titanium base after oil removing is placed in 10% ~ 30% oxalic acid solution etching 0.5-1h of boiling;
(4) coating configuration: Graphene, hydrochloro-auric acid, zirconium nitrate, tin chloride are dissolved in the mixed solution of propyl carbinol or Virahol or both arbitrary proportions according to described mass fraction, add a small amount of concentrated hydrochloric acid, after applying ultrasonic wave, then stir with agitator, particle is dissolved completely;
(5) brushing and sintering: activated coating is coated in uniformly on titanium plate, then dry in an oven, then take out air cooling after sintering; Above-mentioned coating, drying, sintering and cooling step 3 ~ 8 times repeatedly, make to carry painting amount >=5g/m2.
Described step (1), adopt particle diameter to be the granulated glass sphere of 3mm ~ 0.125mm, blasting pressure is 0.7 ~ 0.9MPa.
Described step (2), the Titanium base after sandblasting puts into 80 DEG C of alkaline wash insulation 1h to remove surface and oil contaminant, and this alkaline wash is NaOH, Na2CO3, Na3PO4 mixed solution of 8%, and mass ratio is NaOH:Na2CO3:Na3PO4=5:28:46.
Described step (3), the Titanium base after oil removing is placed in 10% ~ 30% oxalic acid solution etching 0.5-1h of boiling, cleans to be placed in ethanolic soln preserve with deionized water.
In described step (4), the molar content that described Graphene, hydrochloro-auric acid, zirconium nitrate, tin chloride are dissolved in propyl carbinol or Virahol or both mixed solutions is respectively Graphene Graphene:5 ~ 20%, Zr:10 ~ 30%, Au:1 ~ 3%, Sn:55 ~ 85%; The add-on of concentrated hydrochloric acid is 1ml-5ml, after ultrasonic 15min, with more than magnetic stirrer 45min, particle is dissolved completely; Its concentration of metal ions is 0.15 ~ 0.35mol/L.
In described step (5), after Titanium base coating activated coating, dry 10min in baking oven at 120 DEG C, then take out air cooling sinter 10min at 350 ~ 450 DEG C after; After last coating, drying, in the sintering oven at 350 ~ 450 DEG C, be incubated 1h, take out air cooling to room temperature and obtain described oxide anode finished product.
Advantage of the present invention is: by adopting new manufacture craft and the oxide anode of formula, the current density of electrolysis cells is reduced, dwell time of sewage shortens, the simultaneously processing parameter also corresponding reduction of other processing units in treatment system, system bulk can be reduced to a certain extent, reduce system energy consumption.Sewage after adopting electrolytic process Sewage from Ships treatment system of the present invention process meets IMOMEPC.227 (64) resolution requirement.
Accompanying drawing explanation
Fig. 1 is overall formation and the working process schematic diagram for the treatment of system of the present invention.
Description of reference numerals: (1) first holding tank; (2) first sea-water pumps: (3) macerator pump; (4) electric flocculation unit; (5) second holding tanks; (6) second sea-water pumps; (7) electrolysis cells; (8) disappear chlorine unit; (9) ultraviolet lamp; (10) drainage pump; (11) explosion-proof fan; (12) housing.
Embodiment
See Fig. 1, a kind of electrolytic process Sewage from Ships of the present invention treatment system, mainly comprise electric flocculation unit 4, electrolysis cells 7, disappear chlorine unit 8 and associated vessel, pump, valve, pipeline, the outlet of sewage collecting tank 1 is connected by the entrance of macerator pump 3 with electric flocculation unit 4, the outlet of the first sea-water pump 2 is also connected with the entrance of electric flocculation unit 4, and the water out of electric flocculation unit 4 is connected with the entrance of intermediate collection tank 5.The water outlet of intermediate collection tank 5 is connected in series with the chlorine unit 8 that disappears with the entrance of electrolysis cells 7 successively through the second sea-water pump 6, and the sewage after the chlorine unit 8 that disappears disappears chlorine is discharged by drainage pump 10.Sewage draining exit is equipped with in the lower end of sewage collecting tank 1, electric flocculation unit 4, intermediate collection tank 5, the chlorine unit 8 that disappears.Be provided with hydrogen discharge mouth and gas inlet on the top of the chlorine unit 8 that disappears, gas inlet is connected with explosion-proof fan 11.
The working process of above-mentioned treatment system is: sewage collected by sewage collecting tank 1, inside establishes liquid level switch to control startup and the stopping of macerator pump; Sanitary sewage in sewage collecting tank 1 is extracted out by macerator pump 3 and is entered electric flocculation unit 4 after crushed, before entering electric flocculation unit 4, utilize the first sea-water pump 2 to draw a road seawater to mix with sewage (volume ratio is 1:2-1:3), enter electric flocculation unit 4 with the sewage after sea water mixing with certain salinity to process, sewage processes and stops the treatment time in electric flocculation unit 4 is 10-15 minute.The solid precipitation of generation is reacted in the bottom of electric flocculation unit 4 in electric flocculation unit 4, supernatant liquor enters intermediate collection tank 5 from the water out overflow on electric flocculation unit top, sewage in intermediate collection tank 5 is carried out electrolysis by the second sea-water pump 6 suction electrolysis cells 7, and electrolytic current density is 30-48mA/cm
2, electrolysis time 5-20 second.Sewage after electrolysis enters the chlorine unit 8 that disappears subsequently, and under ultraviolet irradiation, it is below the mark that chlorine residue decomposes to IMO, and last sewage is up to standard, and discharges through drainage pump 10.The solid being deposited in the bottom of electric flocculation unit 4 regularly can be discharged and be carried out dewatering, packing, and transports to and be for further processing on the bank.In alternate embodiment of the present invention, can mix with the sewage after pulverizing with salt brine solution, blending ratio is identical with seawater scheme.
The electrode material therefor of described electric flocculation unit 4 is aluminium sheet, iron plate or stainless steel plate etc.Electricity flocculation unit 4 handling principle is: anode produces aluminum ion or ferrous ion (Al under electrochemical action
3+or Fe
2+), the hydroxide radical (OH in aluminum ion and water
-) combine generation aluminium hydroxide floss (Al (OH)
3), ferrous ion is oxidized to iron ion (Fe after generating
3+), the hydroxide radical (OH in iron ion and water
-) combine generation ironic hydroxide floss (Fe (OH)
3), it also precipitates by suspended solids and insoluble organism thereof in this floss absorption effluent from water, thus plays and purify waste water, reduce COD, BOD
5, TSS, total phosphorus and total nitrogen effect.In the present invention, electricity flocculation current density is 10-30mA/cm
2, sewage residence time in electric flocculation unit is 10-15 minute.
Described electrolysis cells 7 anode used is metal oxide anode described in invention, and negative electrode is titanium plate.When the sewage with certain salinity is by electrolyzer, negative electrode, anode generation electrochemical reaction produce clorox, and sewage directly contacts with electrode surface simultaneously, and in water, most of organism is carbonic acid gas and water by direct oxidation under the effect of electrode.COD, BOD of sewage
5and total nitrogen is low through the laggard step-down of electrolysis cells process, the clorox of generation is killed the intestinal bacteria in sewage.During electrolysis, current density is 30-48mA/cm
2.
The Main Function of the described chlorine unit 8 that disappears eliminates the chlorine residue in the water after electrolysis, makes the residual chlorine concentration before discharging of the sewage after process up to standard, and sewage is by the stop in chlorine unit that disappears simultaneously, makes clorox thoroughly kill intestinal bacteria in water.The chlorine unit main operational principle that disappears adopts the ultraviolet lamp tube of certain power to irradiate the sewage containing clorox, and hypochlorous acid or clorox decompose under ultraviolet irradiation.
All the time explosion-proof fan 11(a preparation and a use is had in treating processes) in the chlorine unit 8 that disappears, blast air, the hydrogen that electrolysis is produced is taken out of by air the chlorine unit that disappears and is disposed to safety zone.
The steering logic of whole treatment system by pre-setting, is controlled automatically by housing 12.
Oxide anode used in electrolysis cells 7 of the present invention and preparation method thereof is described as follows:
Oxide anode is: coating consists of Ti/Graphene-Au-ZrO
2-SnO
2, activated coating is by Graphene, Au, ZrO
2, SnO
2composition, content is respectively Graphene:5 ~ 20%, Zr:10 ~ 30%, Au:1 ~ 3%, Sn:55 ~ 85%, carries painting amount>=5g/m
2.
Preparation technology is as follows:
A () sandblasting, selects titanium plate as the body material of oxide anode, carry out sandblasting to increase surfaceness to matrix, and sandblasting adopts particle diameter to be the granulated glass sphere of 3mm ~ 0.125mm, and blasting pressure is 0.7 ~ 0.9MPa.Adopt this blasting craft, make matrix surface have larger surfaceness, the anodic surface toughness of preparation is increased, effective active surface-area is larger, when in applying same current situation, actual loaded reduces in the current density of anode, thus extends the life-span of anode.And the anodic surface toughness of preparation is large, cyclic voltammetric electricity Q obviously increases, and improves electro catalytic activity.
B () oil removing, the Titanium base after sandblasting puts into 80 DEG C of alkaline wash insulation 1h to remove surface and oil contaminant.Alkaline wash is NaOH, Na of 8%
2cO
3, Na
3pO
4mixed solution, wherein mass ratio is NaOH:Na
2cO
3: Na
3pO
4=5:28:46.
C () etches, the Titanium base after oil removing is placed in 10 ~ 30% oxalic acid solution etching 0.5-1h of boiling, cleans to be placed in ethanolic soln preserve with deionized water.Anode substrate etching time of the present invention is short, saves the treatment time.
D () coating configures, a certain amount of Graphene, hydrochloro-auric acid, zirconium nitrate, tin chloride are dissolved in propyl carbinol or Virahol or both mixed solutions, content is respectively Graphene:5 ~ 20%, Zr:10 ~ 30%, Au:1 ~ 3%, Sn:55 ~ 85%, adds a small amount of concentrated hydrochloric acid, after ultrasonic 15min, with more than magnetic stirrer 45min, particle is dissolved completely.Its concentration of metal ions is 0.15 ~ 0.35mol/L.
E () brushing and sintering, brush uniformly by activated coating on titanium plate, then dry 10min in baking oven at 120 DEG C, then take out air cooling sinter 10min at 350 ~ 450 DEG C after.Repeatedly apply afterwards, dry, sintering and cooling step 3 ~ 8 times, make to carry a painting amount>=5g/m
2.After last coating, drying, in the sintering oven at 350 ~ 450 DEG C, be incubated 1h, take out air cooling and obtain Ti/Graphene-Au-ZrO to room temperature
2-SnO
2anode.Anode sintering temperature in the present invention is lower, greatly reduces energy consumption.
Use the treatment effect for the treatment of system process vessel sewage of the present invention as shown in the table.Several processing parameters of sewage in electric flocculation unit 4 and electrolysis cells 7 are as follows:
Example one:
Seawater (salt solution) mixes with sewage (volume ratio is 1:3), and sewage processes and stops the treatment time in electric flocculation unit is 12 minutes, and electricity flocculation current density is 20mA/cm
2.Electrolytic current density is 48mA/cm
2, electrolysis time 20 seconds.
Example two:
Seawater (salt solution) mixes with sewage (volume ratio is 1:2), processes that to stop the treatment time be 15 minutes with sewage in electric flocculation unit, and electricity flocculation current density is 10mA/cm
2.Electrolytic current density is 40mA/cm
2, electrolysis time 10 seconds.
Example three:
Seawater (salt solution) mixes with sewage (volume ratio is 1:3), processes that to stop the treatment time be 10 minutes with sewage in electric flocculation unit, and electricity flocculation current density is 30mA/cm
2.Electrolytic current density is 30mA/cm
2, electrolysis time 5 seconds.
Treatment effect:
Claims (8)
1. an electrolytic process Sewage from Ships treatment system, it is characterized in that, comprise electric flocculation unit, electrolysis cells, disappear chlorine unit and associated vessel, pump, valve, pipeline, the outlet of sewage collecting tank is connected by the entrance of macerator pump with electric flocculation unit, first seawater pump outlet is also connected with the entrance of electric flocculation unit, and the water out of electric flocculation unit is connected with the entrance of intermediate collection tank; The water outlet of intermediate collection tank is connected with the chlorine units in series that disappears with the entrance of electrolysis cells successively through the second sea-water pump, and the sewage after the chlorine unit that disappears disappears chlorine is discharged by drainage pump; Sewage draining exit is equipped with in the lower end of sewage collecting tank, electric flocculation unit, intermediate collection tank, the chlorine unit that disappears; Be provided with hydrogen discharge mouth and gas inlet on the top of the chlorine unit that disappears, gas inlet is connected with explosion-proof fan.
2. electrolytic process Sewage from Ships treatment system according to claim 1, it is characterized in that, described electrolysis cells comprises electrolyzer, oxide anode and negative electrode, arranges oxide anode and negative electrode in electrolyzer; This oxide anode comprises the activated coating on Titanium base and surface thereof, and described activated coating is made up of Graphene, Au, ZrO2 and SnO2, and the molar fraction of each composition is respectively Graphene:5 ~ 20%, Au:1 ~ 3%, Zr:10 ~ 30%, Sn:55 ~ 85%, carries painting amount>=5g/m
2.
3. electrolytic process Sewage from Ships treatment system according to claim 2, it is characterized in that, the preparation method of described oxide anode comprises the following steps:
(1) sandblasting: sandblasting is carried out to increase surfaceness to Titanium base;
(2) oil removing: the greasy dirt of the titanium-based surface after removing sandblasting;
(3) etch: the Titanium base after oil removing is placed in 10% ~ 30% oxalic acid solution etching 0.5-1h of boiling;
(4) coating configuration: Graphene, hydrochloro-auric acid, zirconium nitrate, tin chloride are dissolved in the mixed solution of propyl carbinol or Virahol or both arbitrary proportions according to described mass fraction, add a small amount of concentrated hydrochloric acid, after applying ultrasonic wave, then stir with agitator, particle is dissolved completely;
(5) brushing and sintering: activated coating is coated in uniformly on titanium plate, then dry in an oven, then take out air cooling after sintering; Above-mentioned coating, drying, sintering and cooling step 3 ~ 8 times repeatedly, make to carry painting amount >=5g/m2.
4. electrolytic process Sewage from Ships treatment system according to claim 3, is characterized in that, described step (1), and adopt particle diameter to be the granulated glass sphere of 3mm ~ 0.125mm, blasting pressure is 0.7 ~ 0.9MPa.
5. electrolytic process Sewage from Ships treatment system according to claim 3, it is characterized in that, described step (2), Titanium base after sandblasting puts into 80 DEG C of alkaline wash insulation 1h to remove surface and oil contaminant, this alkaline wash is NaOH, Na2CO3, Na3PO4 mixed solution of 8%, and mass ratio is NaOH:Na2CO3:Na3PO4=5:28:46.
6. electrolytic process Sewage from Ships treatment system according to claim 3, it is characterized in that, described step (3), the Titanium base after oil removing is placed in 10% ~ 30% oxalic acid solution etching 0.5-1h of boiling, cleans to be placed in ethanolic soln preserve with deionized water.
7. electrolytic process Sewage from Ships treatment system according to claim 3, it is characterized in that, in described step (4), the molar content that described Graphene, hydrochloro-auric acid, zirconium nitrate, tin chloride are dissolved in propyl carbinol or Virahol or both mixed solutions is respectively Graphene Graphene:5 ~ 20%, Zr:10 ~ 30%, Au:1 ~ 3%, Sn:55 ~ 85%; The add-on of concentrated hydrochloric acid is 1ml-5ml, after ultrasonic 15min, with more than magnetic stirrer 45min, particle is dissolved completely; Its concentration of metal ions is 0.15 ~ 0.35mol/L.
8. electrolytic process Sewage from Ships treatment system according to claim 3, it is characterized in that, in described step (5), after Titanium base coating activated coating, dry 10min in baking oven at 120 DEG C, then take out air cooling sinter 10min at 350 ~ 450 DEG C after; After last coating, drying, in the sintering oven at 350 ~ 450 DEG C, be incubated 1h, take out air cooling to room temperature and obtain described oxide anode finished product.
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| CN106430452A (en) * | 2016-12-13 | 2017-02-22 | 青岛双瑞海洋环境工程股份有限公司 | Electrolytic method based ship ballast water and domestic wastewater integrated treatment system |
| CN114025867A (en) * | 2019-06-27 | 2022-02-08 | 迪诺拉水务技术有限责任公司 | Method and system for marine wastewater treatment |
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|---|---|
| CN105036423B (en) | 2017-05-10 |
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