CN105036423B - Electrolytic treatment system of ship domestic sewage - Google Patents
Electrolytic treatment system of ship domestic sewage Download PDFInfo
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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 electrolysis Sewage from Ships processing system, belongs to marine environment engineering field.
Background technology
With developing on an unprecedented scale for shipping business and ocean development, the pollution of marine environment is also increasingly severe, and the mankind are to ocean
The protection of environment also pay attention to day by day.Because brought Sewage from Ships pollution problem of transporting by sea also gradually causes the pass of people
Note.Ship, as the vehicles in shipping, is a kind of mobile pollution source, and the discharge of Sewage from Ships is to ocean and inland river
Affect, can not be ignored with the increase of ships quantity.
In order to strictly control the discharge of Sewage from Ships, International Maritime Organization（IMO）Formulated from 1976 to 2012
A series of relevant criterions and directive/guide, wherein newest IMO resolutions（MEPC.227(64)）Will in 1 day January in 2016 reality
Apply.The concrete IMO emission requests that it is provided by resolution that are shown in Table -1.Some existing Technology of Ship Domestic Sewage Treatment can not meet IMO
Newest Sewage from Ships processes standard, therefore, it is necessary to be improved to existing treatment technology and device or develop new
Treatment technology.
The IMO Sewage from Ships of table -1. puts requirement
At present Technology of Ship Domestic Sewage Treatment main both at home and abroad is biochemical process（Activated sludge process, MBR methods）And electrification
Method.Biochemical process is under certain condition, using decomposition digestion of the microorganism to organic matter in sanitary sewage, to generate to ring
The harmless carbon dioxide in border and water, so as to reach the purpose to sewage purification；Electrochemical method mainly utilizes electrochemical method pair
Organic matter in sewage carries out physical removal or direct oxidation, reduces COD and BOD in water5Value, while producing oxidant, kills
Escherichia coli in water.In addition, also needing to process chlorine residue in water so as to reach discharge standard.
Although biochemical process treatment technology and system number of applications are more, there is that processing meanss volume is big, cannot process ash
Water, water resistant power load variability is poor, need special messenger be responsible for safeguard culture bacterium the shortcomings of.Electrochemical process mainly adopts electrolysis tech
Sewage is processed, the technical finesse effect stability, high degree of automation, but the technology still needs to further improve electrolysis
Sewage efficiency, extends electrode life, reduces system energy consumption, further increases the stability of a system.
Oxide anode is the core component that electrolysis processes sanitary sewage.High catalytic performance and stable electrode material are
The core and research emphasis for the treatment of ship domestic sewage through electrolytic process.Ti base precious metal oxides have excellent electro catalytic activity,
It is widely used and research.Particularly nineteen sixty-five Dutchman successfully develops Ti base RuO2Since coated anode, anode
The extensive work of research just launches around metal oxide.
For processing the oxide anode material of sanitary sewage, should typically possess following requirement：With good electric conductivity；
Life-span length, has good electrocatalysis characteristic to anode reaction.At present, a fatal defects of oxide anode are service life
Short, the main cause of electrode inactivation is that Titanium base is oxidized, one layer of passivating film of Titanium base Surface Creation, or active material is de-
Fall or be dissolved.In recent years numerous researchers are in order to solve this problem, it is proposed that many schemes.Female et al. introduction is wherein stood perhaps
A kind of method for preprocessing metal oxide anode substrate, by matrix is carried out processing the oxide anode that makes preparation have compared with
Good stability, but in the patent pre-treating technology time-consuming, high energy consumption, such as oxalic acid etch period is long, and blasting craft is not good
The problems such as.The oxide of Sn, Sb such as Shi Yanhua strengthens the adhesion of active layer and matrix as intermediate layer, and delays oxygen pair
Passivation (the Effect of SbOx+SnO2 Intermediate Layer on the Properties of of matrix
Ti-based MnO2 Anode[J].Acta Phys. Chim.Sin.,2007,23(10):1553-1559.), but be to increase
The content in intermediate layer can reduce oxygen evolution potential, and the application to titanium base oxide anode is unfavorable, is especially processing sanitary sewage
During, such as oxygen evolution potential is low to be unfavorable for that organic matter is oxidized anodically and is beneficial to precipitated oxygen, so as to reduce current efficiency.
The content of the invention
The present invention provides a kind of electrolysis Sewage from Ships processing system, to solve current electrolysis method Sewage from Ships
The short life and electrolytic efficiency that oxide anode in processing system is present needs the problem for further improving, and finally makes process
Sewage index afterwards meets IMO MEPC.227 (64) resolutions and requires.
The technical scheme is that：A kind of electrolysis Sewage from Ships processing system, it is characterised in that including electricity wadding
Solidifying unit, electrolysis cells, disappear chlorine unit and associated vessel, pump, valve, pipeline, and the outlet of sewage collecting tank is by macerator pump and electricity
The entrance connection of flocculation unit, the outlet of the first sea water pump is also connected with the entrance of electric flocculation unit, and the water of electric flocculation unit goes out
Mouth is connected with the entrance of intermediate collection tank；The delivery port of intermediate collection tank through the second sea water pump successively with the entrance of electrolysis cells
Chlorine unit is connected in series with disappearing, and the sewage Jing after the chlorine unit that disappears disappears chlorine is discharged by drainage pump；In sewage collecting tank, electric flocculation list
Unit, intermediate collection tank, the lower end of the chlorine unit that disappears are equipped with sewage draining exit；Hydrogen discharge mouth and air are provided with the top of the chlorine unit that disappears
Entrance, air intake is connected with explosion-proof fan.
Described electrolysis cells include electrolytic cell, oxide anode and negative electrode, in electrolytic cell arrange oxide anode and
Negative electrode；The oxide anode includes the active coating on Titanium base and its surface, described active coating by Graphene, Au,
ZrO2 and SnO2 is constituted, and the molar fraction of each composition is respectively Graphene：5～20%, Au:1～3%, Zr:10～30%, Sn:
55～85%, carry painting amount >=5 g/m2。
The preparation method of described oxide anode is comprised the following steps：
（1）Sandblasting：Titanium base is carried out blasting treatment to increase surface roughness；
（2）Oil removing：Remove the greasy dirt of the titanium-based surface after blasting treatment；
（3）Etching：Titanium base after oil removing is placed in 10%～30% oxalic acid solution etching 0.5-1h of boiling；
（4）Coating is configured：Graphene, gold chloride, zirconium nitrate, stannic chloride are dissolved in into n-butanol according to described mass fraction
Or in isopropanol or both the mixed liquor of arbitrary proportion, a small amount of concentrated hydrochloric acid is added, after applying ultrasonic wave, then stirred with agitator
Mix, be completely dissolved particle；
（5）Brush and sinter：Active coating is uniformly coated in titanium plate, is then dried in an oven, after re-sintering
Take out air cooling；Above-mentioned coating, drying, sintering and cooling step 3～8 times repeatedly, make load painting amount >=5g/m2.
Described step（1）, adopt particle diameter for 3mm～0.125mm bead, blasting pressure be 0.7～0.9MPa.
Described step（2）, the Titanium base after blasting treatment is put into 80 DEG C of alkali wash waters and is incubated 1h to remove surface and oil contaminant, should
Alkali wash water is 8% NaOH, Na2CO3, Na3PO4 mixed liquor, and mass ratio is NaOH:Na2CO3:Na3PO4 =5:28:46.
Described step（3）, the Titanium base after oil removing be placed in boiling 10%～30% oxalic acid solution etching 0.5-1h, spend
Ionized water is placed in ethanol solution after cleaning and preserves.
Described step（4）In, described Graphene, gold chloride, zirconium nitrate, stannic chloride be dissolved in n-butanol or isopropanol or
Molar content in the mixed liquor of both persons is respectively Graphene Graphene：5 ~ 20%, Zr:10 ~ 30%, Au:1 ~ 3%, Sn:55~
85%；The addition of concentrated hydrochloric acid is 1ml-5ml, after ultrasonic 15min, with more than magnetic stirrer 45min making particle completely molten
Solution；Its concentration of metal ions is 0.15 ~ 0.35mol/L.
Described step（5）In, after Titanium base coating active coating, it is dried 10min in baking oven at 120 DEG C, then
Sinter at 350～450 DEG C after 10min and take out air cooling；After last time coating, drying, in the sintering furnace at 350～450 DEG C
Insulation 1h, taking-up is air cooled to room temperature and obtains described oxide anode finished product.
It is an advantage of the invention that：By the oxide anode using new manufacture craft and formula, the electricity of electrolysis cells is made
Current density is reduced, and dwell time of sewage shortens, while the processing parameter of other processing units is also accordingly reduced in processing system, can
To reduce system bulk to a certain extent, system energy consumption is reduced.Jing is using at electrolysis Sewage from Ships of the present invention
Sewage after the process of reason system meets IMO MEPC.227 (64) resolutions and requires.
Description of the drawings
Fig. 1 is that the overall of processing system of the present invention is constituted and course of work schematic diagram.
Description of reference numerals：(1) first collecting tank；(2) first sea water pumps：(3) macerator pump；(4) electric flocculation unit；(5)
Second collecting tank；(6) second sea water pumps；(7) electrolysis cells；(8) disappear chlorine unit；(9) uviol lamp；(10) drainage pump；(11) prevent
Quick-fried blower fan；(12) switch board.
Specific embodiment
Referring to Fig. 1, a kind of electrolysis Sewage from Ships processing system of the invention mainly includes electric flocculation unit 4, electrolysis
Unit 7, disappear chlorine unit 8 and associated vessel, pump, valve, pipeline, and the outlet of sewage collecting tank 1 is by macerator pump 3 and electric flocculation unit
4 entrance connection, the outlet of the first sea water pump 2 is also connected with the entrance of electric flocculation unit 4, the water out of electric flocculation unit 4 and
The entrance connection of intermediate collection tank 5.The delivery port of intermediate collection tank 5 through the second sea water pump 6 successively with the entrance of electrolysis cells 7
Chlorine unit 8 is connected in series with disappearing, and the sewage Jing after the chlorine unit 8 that disappears disappears chlorine is discharged by drainage pump 10.In sewage collecting tank 1, electricity wadding
Solidifying unit 4, intermediate collection tank 5, the lower end of the chlorine unit 8 that disappears are equipped with sewage draining exit.Hydrogen discharge is provided with the top of the chlorine unit 8 that disappears
Mouth and air intake, air intake is connected with explosion-proof fan 11.
The course of work of above-mentioned processing system is：Sewage collecting tank 1 collects sewage, inside sets liquid-level switch control macerator pump
Start and stop；Sanitary sewage in sewage collecting tank 1 is extracted out by macerator pump 3 and enter after crushed electric flocculation unit 4, into electricity
Before flocculation unit 4, draw seawater all the way using the first sea water pump 2 and mix with sewage（Volume ratio is 1:2-1:3）, after sea water mixing
Sewage with certain salinity is processed into electric flocculation unit 4, and sewage processes stop process time in electric flocculation unit 4
For 10-15 minutes.The solids of sedimentation of generation is reacted in electric flocculation unit 4 in the bottom of electric flocculation unit 4, supernatant is from electricity wadding
The water out overflow on solidifying unit top is entered in intermediate collection tank 5, and the sewage in intermediate collection tank 5 is by the suction of the second sea water pump 6
Electrolysis cells 7 are electrolysed, and electrolytic current density is 30-48mA/cm2, the electrolysis time 5-20 seconds.Sewage after electrolysis is with laggard
Enter to disappear chlorine unit 8, and under ultraviolet irradiation, chlorine residue decomposes to that IMO is below the mark, and last sewage is up to standard, and Jing drainage pumps 10
Discharge.It is deposited in the solid of the bottom of electric flocculation unit 4 and can periodically discharges and be dehydrated, packed, and transports to and carry out on the bank next
Step process.In the alternate embodiment of the present invention, can with saline solution with crush after sewage mix, mixed proportion and extra large
Water scheme is identical.
The electrode material therefor of described electric flocculation unit 4 is aluminium sheet, iron plate or corrosion resistant plate etc..At electric flocculation unit 4
Managing principle is：Anode produces aluminium ion or ferrous ion under electrochemical action（Al3+Or Fe2+）, the hydrogen-oxygen in aluminium ion and water
Root（OH-）With reference to generation aluminium hydroxide floccule（Al(OH)3）, after ferrous ion generation iron ion is oxidized to（Fe3+）, iron from
Hydroxyl in son and water（OH-）With reference to generation iron hydroxide floccule（Fe(OH)3）, suspend in the floccule absorption effluent solid
Body and its insoluble organic matter simultaneously precipitate it from water, so as to playing purification sewage, reducing COD, BOD5, TSS, total phosphorus
And the effect of total nitrogen.Electric flocculation current density is 10-30mA/cm in the present invention2, sewage time of staying in electric flocculation unit is
10-15 minutes.
Anode used by described electrolysis cells 7 is metal oxide anode described in invention, and negative electrode is titanium plate.When with one
When the sewage for determining salinity passes through electrolytic cell, there is electrochemical reaction and produce sodium hypochlorite in negative electrode, anode, while sewage and electrode table
Face directly contact, most of organic matter is carbon dioxide and water by direct oxidation in the presence of electrode in water.The COD of sewage,
BOD5And total nitrogen is further reduced Jing after electrolysis cells process, the sodium hypochlorite of generation is killed to the Escherichia coli in sewage
Go out.During electrolysis, current density is 30-48mA/cm2。
The Main Function of the described chlorine unit 8 that disappears is to eliminate the chlorine residue in the water Jing after electrolysis, makes the sewage after process exist
Residual chlorine concentration before discharge is up to standard, while sewage is by the stop in the chlorine unit that disappears, sodium hypochlorite is thoroughly killed in water
Escherichia coli.The chlorine unit main operational principle that disappears is to irradiate the sewage containing sodium hypochlorite using the ultraviolet lamp tube of certain power,
Hypochlorous acid or sodium hypochlorite decompose under ultraviolet irradiation.
There is explosion-proof fan 11 all the time in processing procedure（A preparation and a use）Air is blasted in the chlorine unit 8 that disappears, electrolysis is produced
Raw hydrogen is taken out of the chlorine unit that disappears by air and is emitted into safety zone.
Whole processing system is automatically controlled by the control logic for pre-setting by switch board 12.
Oxide anode used in the electrolysis cells 7 of the present invention and preparation method thereof is described as follows：
Oxide anode is：Coating consists of Ti/ Graphene- Au- ZrO2-SnO2, active coating by Graphene,
Au, ZrO2, SnO2Composition, content is respectively Graphene：5 ~ 20%, Zr:10 ~ 30%, Au:1 ~ 3%, Sn:55 ~ 85%, load painting amount >=
5 g/m2。
Preparation technology is as follows：
（a）Sandblasting, from titanium plate as the matrix material of oxide anode, carries out blasting treatment to increase surface to matrix
Roughness, blasting treatment adopts particle diameter for the bead of 3mm～0.125mm, and blasting pressure is 0.7～0.9MPa.Using this spray
Sand technique so that matrix surface has larger surface roughness, the anodic surface toughness for making preparation increases, effective active table
Area is bigger, and in the case of same current is applied, actual loaded reduces in the current density of anode, so as to extend the longevity of anode
Life.And the anodic surface toughness for preparing is greatly, cyclic voltammetric electricity Q is significantly increased, and improves electro catalytic activity.
（b）Oil removing, the Titanium base after blasting treatment is put into 80 DEG C of alkali wash waters and is incubated 1h to remove surface and oil contaminant.Alkali wash water is
8% NaOH, Na2CO3、Na3PO4Mixed liquor, wherein mass ratio are NaOH:Na2CO3:Na3PO4 =5:28:46。
（c）Etching, the Titanium base after oil removing is placed in 10 ~ 30% oxalic acid solutions etching 0.5-1h of boiling, is washed with deionized water
It is placed in after net in ethanol solution and preserves.The anode substrate etch period of the present invention is short, saves process time.
（d）Coating configure, by a certain amount of Graphene, gold chloride, zirconium nitrate, stannic chloride be dissolved in n-butanol or isopropanol or
In the mixed liquor of both persons, content is respectively Graphene：5 ~ 20%, Zr:10 ~ 30%, Au:1 ~ 3%, Sn:55 ~ 85%, add few
Amount concentrated hydrochloric acid, after ultrasonic 15min, with more than magnetic stirrer 45min being completely dissolved particle.Its concentration of metal ions is
0.15~0.35mol/L。
（e）Brush and sinter, active coating is uniformly brushed in titanium plate, be then dried in baking oven at 120 DEG C
10min, then take out air cooling after sintering 10min at 350～450 DEG C.Afterwards repeatedly coating, be dried, sintering and cooling step 3～
8 times, make load painting amount >=5g/m2.Last time coating, be dried after, be incubated 1h in the sintering furnace at 350～450 DEG C, take out empty
It is cooled to room temperature and obtains Ti/ Graphene- Au- ZrO2-SnO2Anode.Anode sintering temperature in the present invention is relatively low, drops significantly
Low energy consumption.
The treatment effect for processing vessel sewage using processing system of the present invention is as shown in the table.Sewage is in electric flocculation unit 4
And several processing parameters in electrolysis cells 7 are as follows：
Example one：
Seawater（Salt solution）Mix with sewage（Volume ratio is 1: 3）, sewage process in electric flocculation unit stop process time
For 12 minutes, electric flocculation current density was 20mA/cm2.Electrolytic current density is 48mA/cm2, electrolysis time 20 seconds.
Example two：
Seawater（Salt solution）Mix with sewage（Volume ratio is 1: 2）, when stop process is processed in electric flocculation unit with sewage
Between be 15 minutes, electric flocculation current density be 10mA/cm2.Electrolytic current density is 40mA/cm2, electrolysis time 10 seconds.
Example three：
Seawater（Salt solution）Mix with sewage（Volume ratio is 1: 3）, when stop process is processed in electric flocculation unit with sewage
Between be 10 minutes, electric flocculation current density be 30mA/cm2.Electrolytic current density is 30mA/cm2, electrolysis time 5 seconds.
Treatment effect：
Claims (6)
1. a kind of electrolysis Sewage from Ships processing system, it is characterised in that including electric flocculation unit, electrolysis cells, disappear chlorine
Unit and associated vessel, pump, valve, pipeline, the outlet of sewage collecting tank is connected by macerator pump with the entrance of electric flocculation unit, the
The outlet of one sea water pump is also connected with the entrance of electric flocculation unit, and the water out of electric flocculation unit connects with the entrance of intermediate collection tank
Connect；The delivery port of intermediate collection tank is connected in series successively through the second sea water pump with the entrance and the chlorine unit that disappears of electrolysis cells, Jing
The chlorine unit that the disappears sewage after chlorine that disappears is discharged by drainage pump；In sewage collecting tank, electric flocculation unit, intermediate collection tank, disappear chlorine unit
Lower end be equipped with sewage draining exit；Hydrogen discharge mouth and air intake, air intake and explosion-proof wind are provided with the top of the chlorine unit that disappears
Machine connects；
Described electrolysis cells include electrolytic cell, oxide anode and negative electrode, and oxide anode and negative electrode are arranged in electrolytic cell；
The oxide anode includes the active coating on Titanium base and its surface, and described active coating is by Graphene, Au, ZrO2And SnO2
Composition, the molar content of each composition is respectively Graphene：5%～20%, Au:1%～3%, Zr:10%～30%, Sn:55%～85%,
Carry painting amount >=5g/m2；
The preparation method of described oxide anode is comprised the following steps：
（1）Sandblasting：Titanium base is carried out blasting treatment to increase surface roughness；
（2）Oil removing：Remove the greasy dirt of the titanium-based surface after blasting treatment；
（3）Etching：Titanium base after oil removing is placed in 10%～30% oxalic acid solution etching 0.5-1h of boiling；
（4）Coating is configured：Graphene, gold chloride, zirconium nitrate, stannic chloride are dissolved in into n-butanol or different according to described molar content
In the mixed liquor of propyl alcohol or both arbitrary proportion, a small amount of concentrated hydrochloric acid is added, after applying ultrasonic wave, then stirred with agitator, made
Particle is completely dissolved；
（5）Brush and sinter：Active coating is uniformly coated in titanium plate, is then dried in an oven, taken out after re-sintering
Air cooling；Above-mentioned coating, drying, sintering and cooling step 3～8 times repeatedly, make load painting amount >=5g/m2。
2. electrolysis Sewage from Ships processing system according to claim 1, it is characterised in that described step（1）,
Adopt particle diameter for 3mm～0.125mm bead, blasting pressure be 0.7～0.9MPa.
3. electrolysis Sewage from Ships processing system according to claim 1, it is characterised in that described step（2）,
Titanium base after blasting treatment is put into 80 DEG C of alkali wash waters and is incubated 1h to remove surface and oil contaminant, the alkali wash water be 8% NaOH,
Na2CO3、Na3PO4Mixed liquor, mass ratio is NaOH:Na2CO3:Na3PO4 =5:28:46。
4. electrolysis Sewage from Ships processing system according to claim 1, it is characterised in that described step（3）,
Titanium base after oil removing is placed in 10%～30% oxalic acid solution etching 0.5-1h of boiling, and it is molten that deionized water is placed in ethanol after cleaning
Preserve in liquid.
5. electrolysis Sewage from Ships processing system according to claim 1, it is characterised in that described step（4）
In, described Graphene, gold chloride, zirconium nitrate, stannic chloride are dissolved in rubbing in the mixed liquor of n-butanol or isopropanol or both
You are respectively Graphene at content：5% ~ 20%, Zr:10% ~ 30%, Au:1% ~ 3%, Sn:55%~85%；The addition of concentrated hydrochloric acid is 1ml-
5ml, after ultrasonic 15min, with more than magnetic stirrer 45min being completely dissolved particle；Its concentration of metal ions be 0.15 ~
0.35mol/L。
6. electrolysis Sewage from Ships processing system according to claim 1, it is characterised in that described step（5）
In, after Titanium base coating active coating, 10min is dried in baking oven at 120 DEG C, then sinter 10min at 350～450 DEG C
After take out air cooling；After last time coating, drying, 1h is incubated in the sintering furnace at 350～450 DEG C, taking-up is air cooled to room temperature
Obtain described oxide anode finished product.
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| CN105836851A (en) * | 2015-10-29 | 2016-08-10 | 黄理志 | Graphene based water treatment device and method |
| CN106430452B (en) * | 2016-12-13 | 2023-01-10 | 青岛双瑞海洋环境工程股份有限公司 | Ship ballast water and domestic sewage integrated treatment system based on electrolytic method |
| WO2020264153A1 (en) * | 2019-06-27 | 2020-12-30 | De Nora Water Technologies, LLC | Methods and systems for marine wastewater treatment |
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| KR100883444B1 (en) * | 2008-07-24 | 2009-02-17 | (주) 테크윈 | Apparatus and method for ballast water management |
| CN101792199A (en) * | 2010-02-26 | 2010-08-04 | 厦门市威士邦膜科技有限公司 | Sewage treatment technique |
| CN101914782A (en) * | 2010-07-27 | 2010-12-15 | 武汉大学 | Metallic oxide anode suitable for Fenton system and preparation method thereof |
| CN102350228A (en) * | 2011-07-12 | 2012-02-15 | 上海中科高等研究院 | Nano loaded titanium-based electric catalytic film and preparation method thereof |
| CN102515398B (en) * | 2011-11-30 | 2013-03-27 | 青岛双瑞海洋环境工程股份有限公司 | Method for treating domestic sewage of compound ship |
| CN103236550B (en) * | 2013-04-22 | 2015-07-01 | 陕西煤业化工技术研究院有限责任公司 | Graphene-modified nickel-base composite anode material of solid oxide fuel cell and preparation method thereof |
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