CN101781046A - Ship ballast water processing method combining ozone and photocatalysis - Google Patents
Ship ballast water processing method combining ozone and photocatalysis Download PDFInfo
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- CN101781046A CN101781046A CN200910199015A CN200910199015A CN101781046A CN 101781046 A CN101781046 A CN 101781046A CN 200910199015 A CN200910199015 A CN 200910199015A CN 200910199015 A CN200910199015 A CN 200910199015A CN 101781046 A CN101781046 A CN 101781046A
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Abstract
The invention relates to a ship ballast water processing method combining ozone and photocatalysis, comprising the following steps of: firstly, processing sea water by a coarse filtering device; filtering the sea water by a 50 mum filter; further processing the sea water with an ozone/photocatalysis combined processor; introducing the sea water in a ballast warehouse to become ballast water; backwashing the filter with the sea water after loading the ballast water; reprocessing the ballast water with the ozone/photocatalysis combined processor before discharging; and discharging the ballast water. The method has higher reaction speed, can effectively kill protozoon, algae, germ, spore, and the like smaller than 50 mum with the sterilization time less than 10s and basically uses no chemicals. The invention has the advantages of no secondary pollution, little adverse impact on the environment, small volume of the processing device, low energy consumption, high processing efficiency and wide application range.
Description
Technical field
The invention belongs to the ballast water treatment technical field, particularly the ballast water treatment technology of ozone and photocatalysis coupling.
Background technology
Along with global shipping rapid economy development, boats and ships are more and more, volume becomes bigger and bigger, and ship's speed is also more and more faster.Water ballast is the important assurance of marine operation safety.According to estimates, annual nearly 12,000,000,000 tons of the water ballast that present global boats and ships carry, and along with the development of shipping-trade still in cumulative year after year, be present in the biology of travelling around the world with ship in the ballast water for ship every day above 4500 kinds, even through the voyage of several months, many kinds of bacteriums, plant and animals still can survive in water ballast and the settling thereof.Biotic intrusion that biology in the seagoing vessel water ballast migrating in worldwide caused and epidemic transmission etc. occur repeatedly to ocean environment and human infringement incident, caused the extensive concern of international community, Global Environment Facility's tissue (GlobalEnvironment Facility is called for short GEF) confirms as one of four big threats of harm ocean.International Maritime Organizaton (IMO) has formulated " about the international convention of ballast water for ship and settling management and control " (hereinafter to be referred as " pact ") on February 13rd, 2004, this pact has been done clearly regulation to the processing standard of water ballast (comprising that can survive biological size and quantity, pathogenic agent are biological kind and quantity), for Ballast Management and control provide the foundation of the execution with international law restraint force, came into force in 2009 and progressively compulsory execution." pact " means that effective Treatment of Ships'Ballast Water will become " pass " that boats and ships enter the other country harbour, the boats and ships that can't resolve the water ballast problem can't enter the other country harbour, do not have the oceangoing vessel of ballast water treatment facility will face the awkward condition that can not pull in to shore to berth.Therefore, the purifying treatment correlation technique of seagoing vessel water ballast and the research of equipment and industrialization will have a direct impact China's shipping economy, and each shipping enterprise presses for the problem that adopts correlation technique to solve the ballast water for ship emission compliance.
At present, to existing big quantity research of the treatment technology of water ballast and report, the scope of research is more extensive both at home and abroad, and the treatment technology that relates generally to can be divided into following a few class:
(1) physical treatment process (handling) as adopting heat, ultrasonic wave, ultraviolet ray, silver ions, magnetization etc.;
(2) mechanical treatment process (filtering, improve ship design etc.);
(3) method of chemical treatment (ozone, take out oxygen, chlorination processing etc.);
(4) biological treatment (as in water ballast, add carnivorous or parasitic organism to eliminate).
But up to now, numerous studies confirm that, aforesaid method is more or less existing problems all, have the problem that power consumption is big, cost is high as methods such as the heat of physics method, ultrasonic wave, silver ions, magnetization, the traditional UV method exist kill algae difficulty, sterilization not thoroughly, problem such as poor processing effect; There are great number of issues such as equipment volume is big, boats and ships installation difficulty, equipment running cost height in mechanical process; Chemical method exists chemical employed or that reaction generates that seawater is caused secondary pollution problem; There is the problem of the harm of secular potential source biomolecule, poor controllability in biological process, therefore, can directly make the processing of water ballast satisfy the requirement of International Maritime Organizaton without any above-mentioned single method, that is: safe, reliable and effective, environment allow and expense reasonable.Therefore, above-mentioned existing various technology are optimized integration, redevelopment and adaptability innovation, novel method and technology that the research water ballast is effectively handled are one of current important research directions that presses for development in various countries.
At present requiredly a kind ofly can overcome that the equipment volume that exists in the existing seagoing vessel ballast water treatment technology is big, power consumption is big, sterilization not thoroughly, seawater caused shortcomings such as secondary pollution, poor processing effect, invent the treatment process of the seagoing vessel water ballast of a kind of brand-new high-level efficiency, less energy-consumption, non-secondary pollution, can satisfy the requirement of International Maritime Organizaton, that is: safe, reliable and effective, environment allow and expense reasonable.
Summary of the invention
The present invention proposes ozone and photocatalysis coupling technique processing ballast, and this technological synthesis has utilized the synergy of ozone sterilization, ultra-violet sterilization, the strong oxidation disinfection of photochemical catalysis to come processing ballast.
The present invention is achieved through the following technical solutions:
1. earlier with seawater by the coarse filtration device;
2. again seawater is passed through 50 μ m strainers;
3. further seawater being carried out killing microorganisms by ozone and photocatalysis coupling treater handles;
4. then seawater is fed the ballast storehouse water ballast;
5. after adorning the water ballast end, strainer is carried out back flushing with seawater;
6. before water ballast is discharged, once more by ozone and photocatalysis coupling processor processing;
7. at last water ballast is discharged.
The 3. middle ozone and photocatalysis coupling processor processing process of scheme comprises that ozonizer produces ozone sterilization, the sterilization of ultraviolet source photoirradiation and photocatalyst oxidizes germicidal treatment three parts; Ozonizer comprises the various devices that can utilize air and oxygen to wait to produce ozone; Ultraviolet source comprises xenon lamp and the low pressure mercury lamp that can launch UV-light; UV-light is the ultraviolet light that predominant wavelength is lower than 272nm, and optimum is 254nm; Photocatalyst is specifically to be comprised by ultraviolet ray excited semiconductor light-catalyst: titanium dioxide and through the modifying titanium dioxide of art breading such as nitrogen doping, dye sensitization, zinc oxide, tungstic oxide, Niobium Pentxoxide various photocatalysts such as Cadmium Sulfide, cadmium selenide; Optimum is a titanium dioxide based semiconductor photocatalyst.
Above-mentioned photocatalyst is a powdered form; Load on the load attitude on the propping materials such as glass, pottery, silica gel, resin, graphite, zeolite, stainless steel, nickel, titanium.
The seawater that the 5. middle recoil of above scheme washes discharges on the spot.
Advantage of the present invention is:
1, the present invention combines ozone oxidation sterilization, ultraviolet light irradiation sterilization and the strong oxidation disinfection three's of ozone enhanced photocatalysis synergy, be existing ozone oxidation effect, ultraviolet degradation effect in the reaction process, the ozone enhanced photocatalysis strong oxidation is arranged again, remedied sterilization that conventional ultraviolet technology exists not thoroughly, form the biomutation of anti-ultraviolet; Also got rid of independent ozone treatment method because of tail gas contains potential environment and ecological hazard problem such as a large amount of ozone polluted airs;
2, the present invention adopts O3 to substitute oxygen (or air) in the conventional photocatalytic process as oxygenant, increased the generation of hydroxyl radical free radical greatly, and ozone can shift from the surface of photocatalyst by accelerated electron, reduce the recombination probability in light induced electron-hole, therefore greatly improved speed of response, can effectively kill protozoon less than 50 μ m, algae, bacterium, spore etc., sterilizing time was less than 10 seconds;
3, except the ozone that produce at the scene, substantially not additional any other pharmaceutical chemicals, little that uses to the negative impact of ecotope, and redundant ozone can be resolved into oxygen by ultraviolet rays, so present method do not cause secondary pollution, and is little to the negative impact of ecotope.
4, equipment volume is little, energy consumption is low, processing efficiency is high, applied widely, can adjust treatment scale flexibly by the number of increase and decrease ozone and photocatalysis combining processor, processing power can be at 20-5000m3/h.
5, can degrade in kill microorganisms organic pollutant in the seawater improves the water quality of discharging water ballast.
Description of drawings
Further specify the present invention below in conjunction with the drawings and specific embodiments.
Fig. 1 is a schematic flow sheet of the present invention.
Embodiment
In order to make technique means of the present invention, creation characteristic, to reach purpose and effect is easy to understand,, further set forth the present invention below in conjunction with detailed process.
Detailed process of the present invention is: adopt and can produce an amount of concentration of ozone by ozoniferous ozonizer, by aerating apparatus ozone is fed in the pending water ballast.At first, because O3 itself is exactly a kind of strong oxidizer, can direct oxidation decompose the organic pollutant that comprises algae, germ etc. in the water ballast; Simultaneously, being partly dissolved in the UV-irradiation that is lower than the 272nm ultraviolet rays of can launching that the ozone in the water ballast can also be evenly distributed in the water ballast excites, react and produce great amount of hydroxy group free radical (OH) with water, thereby further the microorganisms such as algae, germ that comprise in the water ballast are carried out oxygenolysis; In addition, being distributed in oxygen O2 or the air that the ozone in the water ballast can also substitute in the conventional light-catalyzed reaction is used as electron acceptor(EA) and participates in photocatalysis oxidation reaction, the ozone that is distributed in the water ballast is adsorbed on the surface that is evenly distributed on the photocatalyst in the water ballast, the energy of being launched by ultraviolet source when photocatalyst is during greater than its forbidden band energy ultraviolet ray excited, electronics on its valence band (e-) is excited and is passed forbidden transition to generate light induced electron (e-) to its conduction band, on valence band, then generate photohole (h+) accordingly, these light induced electrons and photohole have strong reducing power and strong oxidation capacity respectively, their free migrations are during to catalyst surface, light induced electron forms ozone anion with the ozonization that is adsorbed on the Nano semiconductor particle surface, and photohole will be adsorbed on the hydroxide ion and the water of catalyst surface and be oxidized to hydroxyl radical free radical (OH).Wherein, OH has extremely strong oxidisability, and its oxidation capacity is respectively H2O2, O3 106～109 times, can make the thorough mineralising of nearly all organism become innoxious substances such as CO2 and H2O.In the inventive method, adopt O3 to shorten 2-3 doubly during than the oxygen O2 electron acceptor(EA) in the conventional light-catalyzed reaction as the reaction path of electron acceptor(EA), can shift from the TiO2 surface by accelerated electron, reduce the recombination probability in light induced electron-hole, greatly improve oxidation efficiency.Analyze from mechanism, the inventive method should comprise plurality of processes such as ozone oxidation reaction, ozone/UV reactive, photocatalysis oxidation reaction.When entering ozone and photocatalysis coupling treater under the drive of the organic microbial in the water ballast (as algae and bacterium etc.) at current, accumulative great amount of hydroxy group free radical and an amount of ozone are captured the protium (H) in the cytolemma of microorganism etc. rapidly in this treater, the microbial cell film is decomposed, and materials such as further biolytic protein, carbohydrate and DNA, thereby kill microorganisms such as algae in the water ballast and bacterium completely.
The present invention realizes by following technique means: (see figure 1)
At first, seawater filters out the macrobead foreign material through coarse filtration devices such as grids and comprises fish, shellfish etc., again behind the further biology of removing greater than 50 μ m of the strainer of 50 μ m, enter ozone and photocatalysis coupling treater, thoroughly killed during by ozone and photocatalysis coupling treater at water ballast less than the biology of 50 μ m, the water ballast of handling well is at last sent into each ballast tank by pipeline.Each dress water ballast finishes, and strainer will be used the seawater back flushing, and the seawater that back flushing is used all directly returns the ocean in the water ballast loading point, pollutes so the settling in the strainer can not arrive next harbour with ship.When ship arrived next harbour and need get rid of water ballast, water ballast by ozone and photocatalysis coupling treater, was further eliminated term of voyage behind the microorganism that cabin grows once more, can realize the safety dumping of water ballast.The effect of implementing can be weighed with the inactivation ratio of algae decreasing ratio and bacterium, and concrete algae and bacterial concentration can use algae counts method, spectrophotometer method and bacterial cultivation (People's Republic of China's National Standard Marine monitoring standard " GB17378-7-1998) mensuration.
The present invention can be used for killing hydrobionts such as the algae, pathogenic micro-organism of ballast water for ship, and can to the various organic pollutants in the water ballast place to go effect be arranged simultaneously, further is illustrated below in conjunction with specific embodiment:
Embodiment one:
The water ballast of taking from superport harbour, foreign mountain at first via hole diameter is after the strainer of 50 μ m filters, wherein diameter is 2.46 * 103/ml less than the algae concentration of 50 μ m, bacterial concentration is 9.22 * 102/ml, (ozone output＞10g/h), emission predominant wavelength are the low pressure mercury lamp of 254nm wavelength and are the ozone and photocatalysis coupling processor processing 5 seconds of the film-type TiO2 photocatalyst for preparing on the load substrate with the industrially pure titanium sheet that control ozone dosage is 0.5mg/L through adopting commercially available ceramic plate ozonizer.Use algae counts method and UV, visible light spectrophotometer method to detect algae and number of bacteria, wherein diameter does not all detect less than algae and the bacterium of 50 μ m, killing rate is 99.99%, and the water ballast that adopts the inventive method to handle can reach International Maritime Organizaton (IMO) set quota.
Embodiment two:
The water ballast via hole diameter of taking from Xiangshan Bay harbour, Ningbo is after the strainer of 50 μ m filters, contain protozoon, algae, bacterium, spore equal diameter and surpass 4.01 * 104/ml less than the hydrobiont concentration of 50 μ m, and the COD of water ballast is 2.37mg/L, (ozone output＞10g/h), emission predominant wavelength are the low pressure mercury lamp of 254nm wavelength and are that control ozone dosage was 0.5-0.7mg/L after the strong oxidation reactor of photochemical catalysis of the film-type TiO2 photocatalyst for preparing on the load matrix was handled in 5 seconds with spongy porous ceramics through adopting commercially available ceramic plate ozonizer.Detect protozoon, algae and bacterium, the result does not all detect, and killing rate reaches 99.99%; Cultivate water ballast after handling through 3 days bacterial cultivations, do not detect yet, prove that the inventive method can kill spore fully less than the bacterium of 50 μ m; Simultaneously, the COD of ballast seawater drops to 0.26mg/L, and clearance reaches more than 89%.The water ballast that adopts the inventive method to handle can reach International Maritime Organizaton (IMO) set quota.
Embodiment three:
The water ballast via hole diameter of taking from the Ningbo Xiangshan Bay is after the strainer of 50 μ m filters, contain protozoon, algae, bacterium, the spore equal diameter surpasses 3.98 * 104/ml less than the hydrobiont concentration of 50 μ m, and the COD of water ballast is 1.62mg/L, through adopting commercially available ceramic plate ozonizer (ozone output＞10g/h), emission predominant wavelength is the low pressure mercury lamp of 254nm wavelength and is that the glass pellet of 5mm is that control ozone dosage was 0.6-0.8mg/L after the strong oxidation reactor of photochemical catalysis of the film-type TiO2 photocatalyst for preparing on the load matrix was handled for 10 seconds with the diameter.Detect protozoon, algae and bacterium, the result does not all detect, and killing rate reaches 99.99%; Cultivate water ballast after handling through 3 days bacterial cultivations, do not detect yet, prove that the inventive method can kill spore fully less than the bacterium of 50 μ m; Simultaneously, the COD of ballast seawater drops to 0.15mg/L, and clearance reaches more than 90.7%.The water ballast that adopts the inventive method to handle can reach International Maritime Organizaton (IMO) set quota.
More than show and described ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that describes in the foregoing description and the specification sheets just illustrates principle of the present invention; the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (8)
1. ship ballast water processing method combining ozone and photocatalysis is characterized in that, comprises the following steps:
1) earlier with seawater by the coarse filtration device;
2) again seawater is passed through 50 μ m strainers;
3) further seawater being carried out killing microorganisms by ozone and photocatalysis coupling treater handles;
4) then seawater is fed the ballast storehouse water ballast;
5) after the dress water ballast finishes, strainer is carried out back flushing with seawater;
6) before water ballast is discharged, once more by ozone and photocatalysis coupling processor processing;
7) at last water ballast is discharged.
2. water treatment method according to claim 1, it is characterized in that ozone and photocatalysis coupling processor processing process comprises that ozonizer produces ozone sterilization, the sterilization of ultraviolet source photoirradiation and photocatalyst oxidizes germicidal treatment three parts in the described step 3).
3. water treatment method according to claim 2 is characterized in that, described ozonizer comprises the various devices that can utilize air and oxygen to wait to produce ozone.
4. water treatment method according to claim 2 is characterized in that, described UV-light is the ultraviolet light that predominant wavelength is lower than 272nm, and optimum is 254nm.
5. water treatment method according to claim 2 is characterized in that, described photocatalyst is can be by ultraviolet ray excited semiconductor light-catalyst, and optimum is a titanium dioxide based semiconductor photocatalyst.
6. water treatment method according to claim 5 is characterized in that, described photocatalyst is a powdered form.
7. water treatment method according to claim 5 is characterized in that, described photocatalyst is to load on spherical, the sheet on glass, pottery, stainless steel, nickel, the titanium etc., netted, spongiform load attitude.
8. water treatment method according to claim 1 is characterized in that, the seawater that recoil washes in the described step 5) discharges on the spot.
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| CN200910199015A CN101781046A (en) | 2009-11-19 | 2009-11-19 | Ship ballast water processing method combining ozone and photocatalysis |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173485A (en) * | 2010-12-14 | 2011-09-07 | 大连海事大学 | Method for treating ship ballast water by injecting oxygen active particles in transmission pipe |
| CN102649607A (en) * | 2011-12-23 | 2012-08-29 | 广州中船龙穴造船有限公司 | Classification and separation method for impurities of ballast water |
| CN102838242A (en) * | 2011-06-21 | 2012-12-26 | 株式会社神户制钢所 | Sterilization method of seawater, sterilization composition generation device |
| CN103058432A (en) * | 2013-01-18 | 2013-04-24 | 哈尔滨工程大学 | Combined type ballast water treatment device |
| CN104016533A (en) * | 2014-06-03 | 2014-09-03 | 上海交通大学 | Ship ballast water treating method |
| CN105645509A (en) * | 2016-01-11 | 2016-06-08 | 汤奇岳 | Green-energy water, and preparation device and method thereof, and application of green-energy water |
| CN105776688A (en) * | 2016-03-29 | 2016-07-20 | 刘牧 | Treatment method of algae-laden water or high-concentration organic waste water |
| WO2020143112A1 (en) * | 2019-01-10 | 2020-07-16 | 彭斯干 | Seagoing ship exhaust gas cleaning method, ship, and application |
| CN112279438A (en) * | 2020-11-09 | 2021-01-29 | 江苏科技大学 | Ship ballast water treatment process and treatment device |
| CN115259492A (en) * | 2022-07-12 | 2022-11-01 | 大连海事大学 | Photoelectric series ballast water treatment method and application thereof |
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2009
- 2009-11-19 CN CN200910199015A patent/CN101781046A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173485A (en) * | 2010-12-14 | 2011-09-07 | 大连海事大学 | Method for treating ship ballast water by injecting oxygen active particles in transmission pipe |
| CN102173485B (en) * | 2010-12-14 | 2012-07-25 | 大连海事大学 | Method for treating ship ballast water by injecting oxygen active particles in transmission pipe |
| CN102838242B (en) * | 2011-06-21 | 2014-09-17 | 株式会社神户制钢所 | Sterilization method of seawater, sterilization composition generation device |
| CN102838242A (en) * | 2011-06-21 | 2012-12-26 | 株式会社神户制钢所 | Sterilization method of seawater, sterilization composition generation device |
| CN102649607A (en) * | 2011-12-23 | 2012-08-29 | 广州中船龙穴造船有限公司 | Classification and separation method for impurities of ballast water |
| CN103058432A (en) * | 2013-01-18 | 2013-04-24 | 哈尔滨工程大学 | Combined type ballast water treatment device |
| CN104016533A (en) * | 2014-06-03 | 2014-09-03 | 上海交通大学 | Ship ballast water treating method |
| CN105645509A (en) * | 2016-01-11 | 2016-06-08 | 汤奇岳 | Green-energy water, and preparation device and method thereof, and application of green-energy water |
| CN105776688A (en) * | 2016-03-29 | 2016-07-20 | 刘牧 | Treatment method of algae-laden water or high-concentration organic waste water |
| WO2020143112A1 (en) * | 2019-01-10 | 2020-07-16 | 彭斯干 | Seagoing ship exhaust gas cleaning method, ship, and application |
| CN112279438A (en) * | 2020-11-09 | 2021-01-29 | 江苏科技大学 | Ship ballast water treatment process and treatment device |
| CN115259492A (en) * | 2022-07-12 | 2022-11-01 | 大连海事大学 | Photoelectric series ballast water treatment method and application thereof |
| CN115259492B (en) * | 2022-07-12 | 2024-03-05 | 大连海事大学 | Photoelectric serial ballast water treatment method and application thereof |
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Open date: 20100721 |