CN1736798A - Water electrolytic treatment system of ballast for cruising - Google Patents
Water electrolytic treatment system of ballast for cruising Download PDFInfo
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- CN1736798A CN1736798A CN 200510046991 CN200510046991A CN1736798A CN 1736798 A CN1736798 A CN 1736798A CN 200510046991 CN200510046991 CN 200510046991 CN 200510046991 A CN200510046991 A CN 200510046991A CN 1736798 A CN1736798 A CN 1736798A
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Abstract
The invention belongs to the art of electrochemical oxidization. Disclosed is an electrolytic treatment system for shipboard ballast water, by electrolyzing the shipboard ballast water directly in the electrolytic treater, highly-effective oxidant which contains one or more among Cl2, HClO molecule, ClO2, free oxygen and hydroxyl radical, being generated, and by the force of electric field, the creature in shipboard ballast water being killed or deactivated. The online detective element measures the concentration of the generated oxidant and sends an electrical signal to an electrical power controller, which can adjust by said signal the electrolytic voltage or adjust treatment flow capacity by changing the opening of the valve when the ballast pump is a centrifugal pump, to keep the concentration of the oxidant in a right range. The invention can effectively remove microcosmic salt out of seawater, reduce the content of COD and TOD in seawater, and increase the dissolved oxygen in seawater. It improves the quality of seawater.
Description
Technical field
The invention belongs to the electrochemical oxidation technology field, relate to a kind of water electrolytic treatment system of ballast for cruising, is the application in the ballast for cruising water treatment field of electrochemical oxidation skill, electrolysis tech and electric field inactivation technology.
Background technology
The marine species that causes with ballast water for ship is to the infringement of marine environment, organized GlobalEnvironment Facility to be called for short four big one of threaten that GEF confirms as the harm ocean by Global Environment Facility.IMO has passed through " international shipping ballast water and sediment management and control pact " in February, 2004 for this reason.Have at least at present to be no less than 25 kinds of ship ballast water treatment method, but do not have a kind of mono-treatment technology can satisfy five standards that IMO proposes, promptly safe, practical, economic, effective and environment is allowed.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, provide a kind of and can improve ballast water water quality, practical, economy and a kind of water electrolytic treatment system of ballast for cruising of actv. can be killed in the ballast water course of conveying or press down the harmful microorganism of living has realized administering ballast water in the online course of conveying.
The present invention solves the technical scheme that its technology adopts, pump into ballast tank or when ballast tank is discharged outboard, directly carry out electrolytic treatments by electrolytic treater 1 at ballast water for ship, ballast water for ship is primary seawater, its conductivity is 15ms/cm-55ms/cm, and suitable flow range is 2.5m
3/ h-500m
3/ h, electrolytic treater 1 input power supply is AC220V or AC380V, the operating voltage range of electrode is 2V-36V, electrode is withstand voltage: more than or equal to DC25V, the electrode insulation degree: more than or equal to 10k Ω, the distance between negative electrode and the anode is 4.5mm-5.5mm, the negative electrode material therefor is a corrosion-resistant steel, the anode material therefor is the DSA anode, and electrolysis produces multiple high-efficient oxidant, comprises chlorine Cl
2, hypochlorous acid HClO molecule, chlorine dioxide ClO
2, free oxygen O and one or more materials of hydroxyl OH, together with effect of electric field, with the biocidal in the ballast water for ship or press down and live.The electrolytic treatments ballast water for ship, the synergy of the multiple oxidic particle that existing electrolysis produces also comprises effect of electric field.Electrolysis can produce multiple strong oxidizer, comprises hypochlorous acid HClO, hydroxyl HO, hydrogen peroxide H
2O
2, chlorine Cl
2Deng, and these oxidizers are not to act on when killing aquatic organism isolatedly, but mutually promote.Such as, in the environment that chloride ion exists, OH is arranged
-During the source, can generate HOCl by reaction
-, HOCl
-To prolong free radical OH
-Life-span, strengthen inactivating efficacy.In addition, electric field also can kill germ in the water by destroying memebrane protein or electric breakdown.
Ballast water for ship pumps in the process by following step process: external dynamic sea enters electrolytic treater 1 direct electrolytic treatments by ballast pump 4 through outlet valve 8 and treater admission valve 10 through valve control cock 6, control cock 7, enters the respective ballast tanks chamber through ballast clack box 5 then.At this moment, control cock 9 and control cock 12 are closed; Ballast water for ship when ballast tank is got outboard by following step process: the ballast tank seawater is through ballast clack box 5, control cock 9, control cock 7, ballast pump 4, carry out electrolytic treatments through control cock 8 and electrolysis generator admission valve 10 electrolytic treater 1 of flowing through again, by control cock 11, control cock 12 and control cock 13 flow out outboard, this moment, control cock 6 was closed, when carrying out electrolytic treatments, oxidant concentration detecting element 3 can be measured the oxidant concentration that electrolysis produces, and send electric signal to control box 2, control box 2 can adjust the decomposition voltage that applies according to this signal, keep the oxidant concentration that produces in suitable scope.In above-mentioned two processes, electrolytic treater 1 operation of can switching on as required, this moment electrolytic treatments; Or the outage operation, do not carry out electrolytic treatments this moment.
The invention has the beneficial effects as follows, can not only remove the phosphate in the seawater effectively, and reduced the content of sea water COD and TOC, and increased the dissolved oxygen of seawater.Improved the character of seawater.Evidence, directly electrolytic treatments uses the initial chlorine residue of 5.0mg/L to be enough to the bacterium in the seawater, algae and protozoan are killed.During the primary seawater of electrolytic treatments, it is processing with 200mg/L, can produce the methenyl choloride amount is 60 μ g/L much smaller than China's GB drinking water sanitary standard (GB5749-85) governing criterion, safety of operation, practical, economic, with the biocidal in the ballast water for ship or press down the active fruit obviously, meet the environment environmental demands.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples.
Fig. 1 is a system architecture scheme drawing of the present invention.
Among the figure: 1, electrolytic treater, 2., control box, 3, the oxidant concentration detecting element, 4, ballast pump, 5, the ballast clack box, 6, control cock, 7, control cock, 8, outlet valve, 9, control cock, 10, electrolysis generator admission valve, 11, control cock, 12, control cock, 13 control cock.
The specific embodiment
The suitable flow of electrolytic treater 1 is 50m
3/ h, the operating voltage of electrolytic treater 1 is 8V, and the negative electrode of electrolytic treater 1 and the distance between the anode are 4.5mm, and the negative electrode material therefor of electrolytic treater 1 is corrosion-resistant steel 1Cr18Ni9Ti, the coating of the DSA anode of electrolytic treater 1 is a ruthenic oxide, and ballast pump 4 is a centrifugal pump.
Ballast water for ship pumps in the process by following step process: external dynamic sea enters electrolytic treater 1 direct electrolytic treatments by ballast pump 4 through outlet valve 8 and treater admission valve 10 through valve control cock 6, control cock 7, enters the respective ballast tanks chamber through ballast clack box 5 then.At this moment, control cock 9 and control cock 12 are closed; Ballast water for ship when ballast tank is got outboard by following step process: the ballast tank seawater is through ballast clack box 5, control cock 9, control cock 7, ballast pump 4, carry out electrolytic treatments through control cock 8 and electrolysis generator admission valve 10 electrolytic treater 1 of flowing through again, flow out outboard by control cock 11, control cock 12 and control cock 13, this moment, control cock 6 was closed
The mutation analysis that uses the present invention to handle the front and back seawer quality be the results are shown in Table one:
The report of table one seawater quality analytical test
Analysis result: | |||
Seawater is untreated | Handle seawater | ||
Nitrate, Nitrite An orthophosphate salt COD DO salinity TOC suspension Zhuo degree electrical conductivity inorganic nitrogen | 616.9 28.2 72.8 10.2 0.52 8.22 29.432 4.01 8.2 11.9 33.89 717.9 | 379.0 3.1 24.6 4.3 0.36 9.54 29.509 3.50 7.8 11.0 34.48 406.7 | ug/L ug/L ug/L ug/L mg/L mg/L mg/L mg/L ms/cm ug/L |
As follows to last table analysis:
1. nitrate, nitrite and the ammonium salt in the table is the summation of inorganic nitrogen in the water, at China's Seawater Quality Standards (GB3097-1997)
[64]Middle inorganic nitrogen concentration should be controlled at 0.2mg/L (1 class water body), 0.3mg/L (2 class water body), 0.4mg/L (3 class water body), 0.5mg/L (4 class water body).Nitrate, nitrite and ammonium salt concentration before and after handle as can be seen, inorganic nitrogen has obtained removal to a certain degree, and is wherein best with the nitrite treatments effect.Because the 4th phosphate in inorganic nitrogen and the table all is the main matter that causes body eutrophication, be significant therefore to its removal.With reference to the 4th class water body (being applicable to the harborage area, ocean, the ocean exploitation operating area) of Seawater Quality Standards as can be seen, handle the requirement that back three's sum can satisfy 0.5mg/L.
" Pollution From Ships thing effluent standard "
[65]There is not concrete regulation among the GB3552-83.
2. treatment technology also has removal effect preferably to phosphate.Reactive phosphate concentration should be controlled at 15ug/L (1 class water body) in the Seawater Quality Standards, 30ug/L (2 class water body), 30ug/L (3 class water body), 45ug/L (4 class water body).The phosphate index all can satisfy the requirement of all kinds of water bodys before and after also promptly handling, and handles its concentration of back and is minimized.
3.COD reducing substances concentration in the expression water (mainly being pollutants), the reduction of its concentration means that certainly water quality is better.COD concentration should be controlled at 2mg/L (1 class water body) in the Seawater Quality Standards, 3mg/L (2 class water body), 4mg/L (3 class water body), 5mg/L (4 class water body).All pretty good before and after handling in the table.This value much higher (60-120mg/L) in the urban sewage discharge standard.
4.DO (dissolved oxygen) high more water quality that shows is good more, its value is relevant with temperature, salt content, bar pressure etc.(20 degree) this value of 9.54mg/L should be very high concerning general fresh water water body at normal temperatures.
5. salinity, conductivity, suspended matter and turbidity change all not obvious.Last is the inorganic nitrogen in article one just, is the former three sum.
6.TOC be the total organic carbon concentration in the water, the pollutants in the low more expression water is few more.
Annotate: the first kind is applicable to the marine fishery waters, marine natural reserve and rare marine life in imminent danger protected zone.Second class is applicable to the aquaculture district, the bathing beach, the movement overseas or the game preserve of human body direct contact seawater, and with the edible directly relevant industrial pool of the mankind.The 3rd class is applicable to the general industry Water District, the strand Scenic Spot Area.The 4th class is applicable to the harborage area, ocean, the ocean exploitation operating area.
Water sample to electrolytic treater electrolytic treatments 1 is analyzed.Table two to table six is the treatment efficiency testing result.
Table two electrolytic treater 1 detects electrolytic parameter
Date | Sequence number | Flow m 3/h | Initial chlorine residue mg/L | Electric current A | Voltage V |
11.10 | NO.1 | 32 | 2.7 | 130 | 6 |
11.10 | NO.2 | 32 | 3.6 | 160 | 7 |
11.10 | NO.3 | 32 | 4.6 | 190 | 7.6 |
11.10 | NO.4 | 32 | 5.8 | 220 | 8.3 |
Table three electrolytic treater 1 test samples No1 plankton count recording
Sampling volume
265mlThe counting volume
5mlSampling time
2004.11.10
Numbering | Plant name | Latin name | Subtotal | Density is (individual/m 3) |
1 | Bivalve larva ¤ | Bilvalvia | 1 | 200000 |
2 | Calanus sinicus ¤ | Calamus sinicus | 1 | 200000 |
3 | Japan angle eye cyclops ¤ | Corycaeus japonicus | 3 | 600000 |
4 | Cosinodisus zero | Coscinodiscus | 2 | 400000 |
5 | The wise water flea ¤ of little plan | Paracalamus parvus | 1 | 200000 |
6 | Ke Shi spindle water flea ¤ | Acartia | 2 | 400000 |
Annotate:
¤ death; Zero fubaritic (plant can not be divided anyway)
Density: this data system becomes 1m by the 256ml sample
3Number.
Subtotal: 1 is meant 1/5ml
3 are meant 3/5ml
Table four electrolytic treater 1 test samples No2 plankton count recording
Sampling volume
250mlThe counting volume
5mlSampling time
2004.11.10
Numbering | Plant name | Latin name | Subtotal | Density is (individual/m 3) |
1 | Ke Shi spindle water flea ¤ | Acartia clausi | 1 | 200000 |
2 | Cosinodisus zero | Coscinodiscus | 1 | 200000 |
Annotate:
¤ death; Zero fubaritic (plant can not be divided anyway)
Density: this data system becomes 1m by the 250ml sample
3Number.
Subtotal: 1 is meant 1/5ml
Table five electrolytic treater 1 test samples No3 plankton count recording
Sampling volume
275mlThe counting volume
5mlSampling time
2004.11.10
Numbering | Plant name | Latin name | Subtotal | Density is (individual/m 3) |
1 | Cosinodisus zero | Coscinodiscus | 1 | 200000 |
2 | The wise water flea ¤ of little plan | Paracalamus parvus | 1 | 200000 |
Annotate:
¤ death; Zero fubaritic (plant can not be divided anyway)
Density: this data system becomes 1m by the 275ml sample
3Number.
Subtotal: 1 is meant 1/5ml
Table six electrolytic treater 1 test samples No3 plankton count recording
Sampling volume
280mlThe counting volume
5mlSampling time
2004.11.10
Numbering | Plant name | Latin name | Subtotal | Density is (individual/m 3) |
1 | Cosinodisus zero | Coscinodiscus | 1 | 200000 |
2 | Copepods ¤ | Copepoea | 1 | 200000 |
Annotate:
¤ death; Zero fubaritic (plant can not be divided anyway)
Density: this data system becomes 1m by the 280ml sample
3Number.
Subtotal: 1 is meant 1/5ml
From above-mentioned test results, except that the algae of Cosinodisus can not be distinguished anyway, all the other detected plankton and all can be killed.
Till when this paper finalizes a text, about " to the approval guide rule of Ballast Management system "
[77]" ballast water treatment technological project approval guide rule "
[78]Resolutions does not pass through as yet, so the test and the evaluation of apparatus for treating ship ballast water are not still had unified standard.
It should be noted that in addition, bacterium is not cooked culture assays in above-mentioned test, because evidence repeatedly, the initial chlorine residue of 4.0mg/L is enough to whole killing bacterias.In order to determine whether the electrolytic treatments ballast water for ship can produce THMs, our experiment of knowing clearly.Monitoring method adopts headspace gas chromatography.Table seven shows experimental result.The haloform class (TTHMs) that chlorination is handled in the water sample of back is analyzed (headspace gas chromatography) report: the μ g/L of content unit.
The THMs testing result of table heptachlor processing seawater sample
Sequence number | Sample | Methenyl choloride | Carbon tetrachloride | Chlorodibromomethane | Dichloro one | Bromoform | |
1. | Filtering sea (control group) | 0 | 0 | 0 | 0 | 0 | |
2. | Tap water (control group) | 12.913 | 0.0 | 8.243 | 3.605 | 2.182 | |
3. | Filtering sea (processing of 20mg/L effective chlorine) | 0.074 | 0 | 0.069 | 0.869 | 8.022 | |
4. | Filtering sea (processing of 60mg/L effective chlorine) | 0.225 | 0 | 0.193 | 1.766 | 9.418 | |
5. | Contain 10 9/ L tower born of the same parents segasso sea water (processing of 20mg/L effective chlorine) | 0.174 | 0 | 0.123 | 2.201 | 13.400 | |
6. | Contain 10 9/ L tower born of the same parents segasso sea water (processing of 40mg/L effective chlorine) | 0.216 | 0 | 0.198 | 2.602 | 10.650 | |
7. | Contain 10 9/ L tower born of the same parents segasso sea water (processing of 100mg/L effective chlorine) | 1.289 | 0 | 2.412 | 31.343 | 57.141 | |
8. | Contain 10 9/ L tower born of the same parents segasso sea water (processing of 500mg/L effective chlorine) | 7.701 | 0.0 | 50.280 | 235.023 | 43.624 | |
9. | Contain 10 9/ L tower born of the same parents segasso sea water (processing of 1000mg/L effective chlorine) | 17.255 | 0.1 | 158.324 | 318.381 | 44.695 | |
10. | Natural sea-water (1% precipitation) (processing of 50mg/L effective chlorine) | 0.798 | 0.0 | 6.442 | 30.580 | 22.975 | |
11. | Natural sea-water (1% precipitation) (processing of 100mg/L effective chlorine) | 0.802 | 0.0 | 6.696 | 32.258 | 28.337 | |
12. | Natural sea-water (1% precipitation) (processing of 200mg/L effective chlorine) | 2.737 | 0.0 | 17.810 | 67.321 | 29.310 |
Stipulate in many national water quality standard for drinking waters that TTHMs is less than 100 μ g/L (ppb).China's GB drinking water sanitary standard (GB5749-85) governing criterion is 60 μ g/L.
From table seven as seen, during the primary seawater of electrolytic treatments, be processing with 200mg/L, can produce the methenyl choloride amount much smaller than 60 μ g/L.
That is to say, the problem of being concerned about most with regard to people that can produce chloroform, from security standpoint and environmental angle, the electrolytic treatments ballast water for ship, environment can be accepted and allow.
Claims (9)
1, water electrolytic treatment system of ballast for cruising, it is characterized in that, pump into ballast tank or when ballast tank is discharged outboard at ballast water for ship, directly carry out electrolytic treatments by electrolytic treater (1), ballast water for ship is primary seawater, its conductivity is 15ms/cm-55ms/cm, and suitable flow range is 2.5m
3/ h-500m
3/ h, electrolytic treater (1) input power supply is AC220V or AC380V, the operating voltage range of electrode is DC 2V-36V, electrode is withstand voltage: more than or equal to DC25V, the electrode insulation degree: more than or equal to 10k Ω, the distance between negative electrode and the anode is 4.5mm-5.5mm, the negative electrode material therefor is a corrosion-resistant steel, the anode material therefor is the DSA anode, and electrolysis produces multiple oxidizer, comprises chlorine Cl
2, hypochlorous acid HClO molecule, chlorine dioxide ClO
2, free oxygen O and one or more materials in the hydroxyl OH material, together with effect of electric field, with the biocidal in the ballast water for ship or press down to live, ballast water for ship pumps in the process by following step process: external dynamic sea enters electrolytic treater (1) directly electrolytic treatments by ballast pump (4) through outlet valve (8) and treater admission valve (10) through valve control cock (6), control cock (7), enters the respective ballast tanks chamber through ballast clack box (5) then.At this moment, control cock (9) and control cock (12) are closed; Ballast water for ship when ballast tank is got outboard by following step process: the ballast tank seawater is through ballast clack box (5), control cock (9), control cock (7), ballast pump (4), pass through control cock (8) and electrolysis generator admission valve (10) electrolytic treater (1) of flowing through again and carry out electrolytic treatments, by control cock (11), control cock (12) and control cock (13) flow out outboard, control cock this moment (6) is closed, when carrying out electrolytic treatments, oxidant concentration detecting element (3) can be measured the oxidant concentration that electrolysis produces, and sending electric signal to control box (2), control box (2) can adjust the decomposition voltage that applies according to this signal.
2, water electrolytic treatment system of ballast for cruising according to claim 1 is characterized in that, described electrolytic treater (1) is flat or cylinder type.
3, water electrolytic treatment system of ballast for cruising according to claim 1 is characterized in that, the suitable flow of described electrolytic treater (1) is 50m
3/ h.
4, water electrolytic treatment system of ballast for cruising according to claim 1 is characterized in that, the operating voltage of described electrolytic treater (1) is 8V.
5, water electrolytic treatment system of ballast for cruising according to claim 1 is characterized in that, the distance between described electrolytic treater (1) negative electrode and the anode is 4.5mm.
6, water electrolytic treatment system of ballast for cruising according to claim 1 or 5 is characterized in that the negative electrode material therefor of described electrolytic treater (1) is corrosion-resistant steel 1Crl8Ni9Ti.
7, water electrolytic treatment system of ballast for cruising according to claim 1 or 5 is characterized in that the coating of the DSA anode of described electrolytic treater (1) is platinum plating, ruthenic oxide or tin ash.
8, water electrolytic treatment system of ballast for cruising according to claim 1 is characterized in that, described control box (2) comprises four modules: oxidizer detects, decomposition voltage is regulated, the ballast pump flow is regulated and power supply.
9, water electrolytic treatment system of ballast for cruising according to claim 1 is characterized in that, described ballast pump (4) is a centrifugal pump.
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